Resin composition for low dielectric materials, film for laminated substrates, laminated substrate, method for manufacturing a resin composition for low dielectric materials, method for manufacturing a film for laminated substrates, and method for manufacturing a laminated substrate.

Abstract

The purpose of the present invention is to provide: a resin composition which has a small dielectric constant, a small dielectric loss tangent, high transparency, high solubility and high heat resistance and can be used suitably as a low-dielectric material; a film for a multilayer substrate, in which the resin composition is used; a multilayer substrate; and methods respectively for producing the resin composition, the film and the multilayer substrate. Provided are: a resin composition for a low-dielectric material, which contains a triazine-containing polyether compound having a specific repeating unit; a film for a multilayer substrate; a multilayer substrate; a method for producing a resin composition for a low-dielectric material; a method for producing a film for a multilayer substrate; and a method for producing a multilayer substrate.

Description

[Technical Field]

[0001] The present invention relates to a resin composition for low dielectric materials containing a triazine-containing polyether compound for use as a low dielectric material in electronic devices and the like, a film for laminated substrates, a laminated substrate, a method for producing a resin composition for low dielectric materials, a method for producing a film for laminated substrates, and a method for producing a laminated substrate. This application claims priority based on Japanese Patent Application No. 2021-050547, filed in Japan on March 24, 2021, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Among resin materials, aromatic polyethers are widely used in the automotive and machinery sectors as so-called engineering resins because they have excellent heat resistance and relatively good mechanical strength. Furthermore, development is underway to create novel structures that offer even better engineering resins, achieving both superior heat resistance and thermal stability.

[0003] Patent Document 1 discloses a phenyltriazine compound bonded to an aryl group. This technology aims to provide an aromatic polyether resin that is excellent in heat resistance and thermal stability, as well as in mechanical strength, and can be advantageously used as an engineering resin.

[0004] Meanwhile, as society's communication infrastructure transitions to 5G, high-frequency electromagnetic waves such as microwaves and millimeter waves used in electronic devices are attracting attention, and research into their applications in the communications field and vehicle radar is progressing. Devices using high-frequency electromagnetic waves require low dielectric constant and low dielectric loss tangent for components such as substrates, resonators, filters, and antennas. At the same time, the materials used for these components must also possess a combination of various mechanical properties, such as physical strength and thermal properties. Currently, materials that satisfy these properties include resin materials with added ceramic fillers. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 6-184300 [Overview of the project] [Problems that the invention aims to solve]

[0006] On the other hand, research is underway on organic materials, particularly resin materials, that possess excellent properties for application in electronic devices and components in the high-frequency range. Among these, materials with low dielectric properties and materials with low dielectric loss tangents, which can be used in insulating components and printed circuit boards, are in particularly high demand.

[0007] The inventors searched for resin materials with excellent properties, specifically those with low dielectric properties and low dielectric loss tangents. As a result, they discovered that triazine-containing polyether compounds with a specific structure possess not only excellent mechanical and thermal properties, but also excellent properties as low dielectric constant and low dielectric loss tangent materials, leading to the completion of the present invention.

[0008] This invention has been made in view of the above circumstances, and aims to provide a resin composition that can be suitably used as a low dielectric material because it has a low dielectric constant, a low dielectric loss tangent, high transparency, high solubility, and high heat resistance, as well as a film for laminated substrates using the same, a laminated substrate, and a method for manufacturing the same. [Means for solving the problem]

[0009] To solve the above problems, the present invention has the following aspects. [1] A resin composition for low dielectric materials comprising a triazine-containing polyether compound having repeating units represented by the following general formula (1). [ka] [In formula (1), n ​​is an integer of 2 or more, Ar represents a divalent aromatic group with or without substituents, R represents hydrogen, a linear, branched, or cyclic aliphatic group, an aromatic group with or without substituents, a fluorinated aliphatic group, or a fluorinated aromatic group.] [2] The resin composition for low dielectric materials, wherein the Ar comprises a triazine-containing polyether compound represented by any of the following general formulas (2) to (15). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [3] The resin composition for low dielectric materials comprising a triazine-containing polyether compound having an average degree of polymerization of the repeating unit represented by n in the general formula (1) of 2 to 200. [4] The triazine-containing polyether compound has dielectric constant D k is 2.8 or less, and / or dielectric loss tangent D f The resin composition for low dielectric materials, wherein the ratio is 0.003 or less. [5] The triazine-containing polyether compound is a resin composition for low dielectric materials having a glass transition temperature of 200°C or higher. [6] The resin composition for low dielectric materials comprising the triazine-containing polyether compound and an epoxy resin, a bismaleimide resin, or a cyanate resin. [7] The resin composition for low dielectric materials, further comprising an inorganic filler, a modifier, or a flame retardant. [8] The resin composition for low dielectric materials used in equipment that transmits and receives high-frequency electromagnetic waves with a frequency of 0.1 to 500 GHz. [9] A resin composition for low dielectric materials used in printed circuit boards, flexible printed circuit boards, encapsulants for electronic components, resist inks, conductive pastes, insulating materials, or insulating boards.

[10] A film for a laminated substrate having an insulating material comprising the resin composition for low dielectric material described above on at least one surface.

[11] A laminated substrate comprising two or more of the aforementioned laminated substrate films.

[12] A method for producing the resin composition for the low dielectric material, A method for producing a resin composition for low dielectric materials, comprising mixing a compound represented by the following general formula (16) and a compound represented by the following general formula (17), and polymerizing them to obtain a triazine-containing polyether compound represented by the following general formula (18). [ka] [ka] [ka] [In formulas (16), (17), and (18), n is an integer greater than or equal to 2, and Ar represents a divalent aromatic group with or without substituents. R represents hydrogen, a linear, branched, or cyclic aliphatic group, an aromatic group with or without substituents, a fluorinated aliphatic group, or a fluorinated aromatic group.]

[13] A method for producing a resin composition for a low dielectric material used as an insulating material between layers of a laminated substrate, A method for producing the resin composition for low dielectric materials, comprising mixing the triazine-containing polyether compound, an epoxy resin, a bismaleimide resin or a cyanate resin, a curing accelerator, and an organic solvent.

[14] A method for producing the resin composition for low dielectric materials, further comprising mixing an inorganic filler, a modifier, or a flame retardant.

[15] A method for manufacturing a laminated substrate film, comprising applying an insulating material containing the resin composition for low dielectric material described above to at least one surface of a resin film.

[16] A method for manufacturing a laminated substrate, comprising stacking two or more of the aforementioned films for the laminated substrate. [Effects of the Invention]

[0010] According to the present invention, a resin composition that can be suitably used as a low dielectric material due to its low dielectric constant, low dielectric loss tangent, high transparency, high solubility, and high heat resistance, as well as a film for laminated substrates using the same, a laminated substrate, and a method for manufacturing the same, can be obtained. [Brief explanation of the drawing]

[0011] [Figure 1] This figure shows the FT-IR spectra of Reference Examples 1 to 4 of this embodiment. [Modes for carrying out the invention]

[0012] The resin composition for low dielectric materials and the method for producing the same according to the present invention will be described below with reference to embodiments. However, the present invention is not limited to the following embodiments.

[0013] (Resin composition for low dielectric materials) The resin composition for low dielectric materials of this embodiment comprises a specific triazine-containing polyether compound. Here, a low dielectric material is a material with a low dielectric constant and / or a low dielectric loss tangent. That is, it is a low dielectric constant material or a low dielectric loss tangent material, but hereinafter it will be collectively referred to as a "low dielectric material." The definition of the measurement conditions for dielectric constant will be described later. Low dielectric materials are used in electronic equipment or electronic components where a low dielectric constant and / or a low dielectric loss tangent are required. Parts where a low dielectric constant and / or a low dielectric loss tangent are required are, for example, parts where insulation is required, such as insulating parts such as insulating plates and insulating parts of printed circuit boards. Printed circuit boards also include flexible printed circuit boards. The compounds contained in the material of this embodiment have a low dielectric constant and / or a low dielectric loss tangent, especially at high frequencies, so it is preferable to use them in electronic components and electronic equipment, especially in high-frequency compatible electronic components and electronic equipment.

[0014] The triazine-containing polyether compound included in the resin composition of this embodiment has repeating units represented by the following general formula (1). [ka]

[0015] Here, in formula (1), n ​​is an integer of 2 or more, and Ar is an arylene group, representing a divalent aromatic group with or without substituents. Here, substituents broadly refer to groups of a different group from the group (atomic group) to which they are bonded, and which can be bonded by replacing some atoms (preferably hydrogen) of the group to which they are bonded. Aromatic groups broadly refer to groups that include the structure of aromatic compounds or partially substituted compounds. Aliphatic groups broadly refer to groups that include the structure of non-aromatic organic compounds or partially substituted compounds. In the formula, n represents the number of repeating units of the structure represented by formula (1), and is an integer of 2 or more. As will be described later, the average value of the degree of polymerization n of the triazine-containing polyether compound contained in the resin composition for low dielectric material of this embodiment is the average degree of polymerization, and the value of the average degree of polymerization is preferably 2 to 200, and may be 2 to 100. R is an organic substituent, which may be a hydrogen atom, or a linear, branched, or cyclic aliphatic group. R may also be an aromatic group with or without substituents. Furthermore, R may be any of the aforementioned fluorinated aliphatic groups or any of the aforementioned fluorinated aromatic groups. The degree to which R is fluorinated can be broadly selected, ranging from fluorination of one carbon bond site to fluorination of all carbon bonds except those bonded to the target group. For example, if R is a methyl group, 1 to 3 of the hydrogen atoms of the methyl group may be substituted with fluorine, but 2 to 3 are preferred. In formula (1), R may be the same substituent or different. The above-described chemical structure of the triazine-containing polyether compound contained in the resin composition of this embodiment can be measured by infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), for example. 1 H-NMR, 13 C-NMR, 19 It can be identified by 1F-NMR or elemental analysis, etc.

[0016] Examples of arylene groups on Ar can be appropriately selected from various divalent aromatic residues obtained by abstracting a total of two hydrogen atoms or other substituents from the aromatic ring in various aromatic compounds or aromatic ring-containing compounds. Examples of arylene groups can be appropriately selected from various phenylene groups, naphthylene groups, and biphenylene groups. Ar may also be bonded to other alkyl groups, alkylene groups, alkylidene groups, cycloalkyl groups, cycloalkylene groups, cycloalkylidene groups, aryl groups, arylene groups, fluorinated alkyl groups, fluorinated alkylene groups, fluorinated aryl groups, or fluorinated arylene groups.

[0017] The triazine-containing polyether compound in this embodiment may be a triazine-containing polyether compound in which the Ar is represented by any one of the following general formulas (2) to (15). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0018] Here, regarding Ar represented by each formula, in the above formula, it is a divalent phenol (HO-Ar-OH), formula (2) is BisA, formula (3) is BisAF, formula (4) is BisPHTG, formula (5) is BisPIND, formula (6) is BisC, formula (7) is TMBisA, formula (8) is BisCHP, formula (9) is BisZ, formula (10) is BisP3MZ, formula (11) is BisPCDE, formula (12) is DTPM, formula (13) is BPFL, formula (14) is DMBPFL, and formula (15) may also be represented as TBISRX. When Ar having these structures is used in the resin composition of the present embodiment for a low dielectric material, in particular, a resin composition for a low dielectric material containing a triazine-containing polyether compound having a low dielectric constant, a low dielectric tangent, and high heat resistance can be obtained.

[0019] It is preferable that the average degree of polymerization of the repeating unit represented by n in the general formula (1) of the triazine-containing polyether compound of the present embodiment is 2 to 200. When the average degree of polymerization of the repeating unit represented by n is 2 to 200, a compound having an appropriate molecular weight can be obtained when used as a resin composition for a low dielectric material. The molecular weight of the triazine-containing polyether compound of the present embodiment is, as a guide, when using Ar of the above formulas (2) to (15), the number average molecular weight (M n [[ID=**12**]]) is preferably 3×10 3 ~40×10 4 , and more preferably 3×10 3 ~20×10 4 . The weight average molecular weight (M w ) is preferably 6×10 3 ~40×10 4 , and more preferably 6×10 3 ~40×10 4 . The molecular weight of the compound of the present embodiment can be measured using gel permeation chromatography (GPC) or the like. From this molecular weight and the structure of the above-described compound, the average degree of polymerization can be determined.

[0020] The triazine-containing polyether compound of the present embodiment has a dielectric constant D It should be noted that in the provided text, there is a possible error in the formatting of the molecular weight expressions in - . The correct format might be something like $M_n$ and $M_w$ for number average molecular weight and weight average molecular weight respectively, with proper superscript and subscript notations. However, based on the translation rules, the text has been translated as accurately as possible while maintaining the original format. If you have any further questions or need more clarification, please let me know.k is 2.8 or less, and / or dielectric loss tangent D f It is preferable that the value is 0.003 or less. Here, the dielectric constant D k and dielectric loss tangent D f These are values ​​measured using existing dielectric property measuring devices. Examples of existing dielectric property measuring devices include cavity resonator type devices. Furthermore, in the triazine-containing polyether compound of this embodiment, the dielectric constant D k It is preferable that the dielectric loss tangent D is 2.7 or less. f It is preferably 0.003 or less, and more preferably 0.002 or less. Specifically, another aspect of this embodiment is that the triazine-containing polyether compound has a dielectric constant D k is 2.7 or less and dielectric loss tangent D f It may be 0.002 or less.

[0021] The triazine-containing polyether compound of this embodiment preferably has a glass transition temperature of 200°C or higher, and more preferably 260°C or higher. It is also preferable that the 5% thermal decomposition temperature be between 400 and 600°C. The glass transition temperature of the triazine-containing polyether compound in this embodiment can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), dynamic viscoelasticity measurement (DMA), or the like. The 5% thermal decomposition temperature of the triazine-containing polyether compound in this embodiment is obtained by measuring the weight loss temperature. The weight loss temperature can be measured using, for example, thermogravimetric analysis (TGA).

[0022] The resin composition for low dielectric materials of this embodiment may also preferably contain the triazine-containing polyether compound and an epoxy resin, bismaleimide resin, or cyanate resin. By including an epoxy resin, a resin composition for low dielectric materials with excellent heat resistance, mechanical properties, and dielectric properties can be obtained.

[0023] While there are no particular limitations on the epoxy resin, examples of epoxy resins that yield cured products with excellent heat resistance include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolac type epoxy resin, and naphthol novolac. Epoxy resins such as naphthol aralkyl epoxy resins, naphthol-phenol copolymer novolac epoxy resins, naphthol-cresol copolymer novolac epoxy resins, biphenyl-modified phenol epoxy resins (polyvalent phenol epoxy resins in which a phenol skeleton and a biphenyl skeleton are linked by a bismethylene group), biphenyl-modified naphthol epoxy resins (polyvalent naphthol epoxy resins in which a naphthol skeleton and a biphenyl skeleton are linked by a bismethylene group), alkoxy-group-containing aromatic ring-modified novolac epoxy resins (compounds in which a glycidyl group-containing aromatic ring and an alkoxy-group-containing aromatic ring are linked by formaldehyde), phenylene ether epoxy resins, naphthylene ether epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin epoxy resins, or xanthene epoxy resins may be used. These may be used individually or in combination of two or more types. The bismaleimide resin is not particularly limited, but in terms of obtaining a cured product with excellent heat resistance, for example, diphenylmethane-type bismaleimide resin, metaphenylene-type bismaleimide resin, bisphenol A diphenyl ether-type bismaleimide resin, diphenyl ether-type bismaleimide resin, diphenyl sulfone-type bismaleimide resin, diphenoxybenzene-type bismaleimide resin, or aniline novolac-type bismaleimide resin may be used. These may be used individually or in combination of two or more types. While the cyanate resin is not particularly limited, for example, bisphenol A type cyanate resin, tetramethylbisphenol F type cyanate resin, hexafluorobisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol M type cyanate resin, novolac type cyanate resin, and cyclopentadienylbisphenol type cyanate resin may be used, as they yield cured products with excellent heat resistance. These may be used individually or in combination of two or more types.

[0024] The resin composition for low dielectric materials of this embodiment may further preferably contain an inorganic filler, a modifier, or a flame retardant. As inorganic fillers, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, or magnesium hydroxide may be used. As a modifier, various thermosetting resins and thermoplastic resins can be appropriately selected, but for example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, or polyethylene terephthalate resin, cycloolefin resin, fluororesin, etc. may be used. Flame retardants can be appropriately selected from, for example, halogen compounds, phosphorus-containing compounds, nitrogen-containing compounds, and inorganic flame retardants. Examples include halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolac type epoxy resin; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and cresyldiphenyl phosphate. Phosphate esters such as xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris(2,6-dimethylphenyl) phosphate, and resorcinol diphenyl phosphate; phosphorus atom-containing compounds such as condensed phosphoric acid or ester compounds such as ammonium polyphosphate, polyphosphate amide, red phosphorus, guanidine phosphate, and dialkylhydroxymethylphosphonate; nitrogen atom-containing compounds such as melamine; and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, zinc borate, or calcium borate may also be used.

[0025] The resin composition for low dielectric materials of this embodiment is preferably used in equipment that transmits and receives high-frequency electromagnetic waves with a frequency of 0.1 to 500 GHz. Specifically, the resin composition for low dielectric materials of this embodiment is preferably used in equipment that transmits and receives microwave or millimeter-wave electromagnetic waves. Here, microwaves generally refer to electromagnetic waves with frequencies of 0.25 to 100 GHz, and millimeter waves refer to electromagnetic waves with frequencies of 30 to 300 GHz, and it is even more preferable to use it in equipment that transmits and receives these. The resin composition for low dielectric materials of this embodiment can also be suitably used in equipment that uses electromagnetic waves with frequencies such as 60 GHz used in wireless LANs and 75 to 79 GHz used in vehicle radar. The resin composition for low dielectric materials of this embodiment has a sufficiently low dielectric constant and dielectric loss tangent, making it particularly suitable for use with high-frequency electromagnetic waves.

[0026] The resin composition for low dielectric materials of this embodiment is preferably used in printed circuit boards, flexible printed circuit boards, encapsulants for electronic components, resist inks, conductive pastes, insulating materials, or insulating boards. The resin composition for low dielectric materials of this embodiment has sufficiently low dielectric constant and dielectric loss tangent, making it suitable for use in these components. Furthermore, it is particularly suitable for use in these components in equipment that uses high-frequency electromagnetic waves. More specifically, it can be used as a resin composition for copper-clad laminates, an interlayer insulating material for build-up printed circuit boards, or a build-up film. It can also be used as a resin composition for encapsulating electronic components, a resin composition for resist inks, a binder for friction materials, a conductive paste, a resin casting material, an adhesive, or a coating material such as an insulating paint.

[0027] The resin composition for low dielectric materials of this embodiment is preferably used as an insulating material between layers of a laminated substrate. In this case, the resin composition is preferably prepared by mixing the triazine-containing polyether compound, epoxy resin, bismaleimide resin, or cyanate resin, a curing accelerator, and an organic solvent, as described in the manufacturing method later.

[0028] (Film for laminated substrates) The laminated substrate film of this embodiment has an insulating material containing the resin composition for the low dielectric material on at least one surface. Multiple of these laminated substrate films can be laminated together to form a laminated substrate described later. The film for the laminated substrate consists of a film layer, described later, and an insulating layer having an insulating material. The insulating layer is provided on at least one surface of the film layer by a manufacturing method described later.

[0029] The film layer can be constructed using appropriately selected film materials, such as resin films or metal films. Specifically, it can be formed using polyethylene, polypropylene, polyvinyl chloride, polycycloolefin, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, polyimide, release paper, copper foil, aluminum foil, etc.

[0030] The thickness of the film for the laminated substrate in this embodiment is not particularly limited, but can be selected from a range of 10 to 150 μm, and is preferably in the range of 25 to 50 μm.

[0031] The laminated substrate film of this embodiment may further have a protective film on its surface. The protective film prevents dust and other debris from adhering to the surface of the film layer and insulating layer before use, and prevents scratches from occurring, thereby preventing a decrease in performance such as insulation before use. The constituent material of the protective film may be selected from the same materials as those used for the film layer described above. The thickness of the protective film may be in the range of 1 to 40 μm. Furthermore, the film for the laminated substrate and the protective film may be treated with a matte finish, corona treatment, or release treatment. Furthermore, when the laminated substrate is a conductive laminated substrate or a build-up printed circuit board, and a conductive layer made of a conductor such as metal is laminated with the insulating layer, the combination of the conductive layer and the insulating layer may constitute the film for the laminated substrate.

[0032] The resin composition for low dielectric materials of this embodiment has excellent physical properties, heat resistance, low dielectric constant, and low dielectric loss tangent, and is therefore extremely useful as an insulating material between layers of laminated substrate films in a laminated substrate comprising two or more laminated substrate films. Such insulating materials are preferably manufactured using the resin composition for low dielectric materials and epoxy resin, bismaleimide resin, or cyanate resin as essential components, and further, optionally, by blending in organic solvents and curing accelerators described later.

[0033] (Laminated substrate) The laminated substrate of this embodiment comprises two or more of the laminated substrate films. Preferably, the laminated substrate is formed by laminating the laminated substrate films. The laminated substrate film may be an intermediate layer or a base layer in the laminated substrate. It may also be used as a layer on which circuits are formed or as a layer on which circuits are not formed. Circuit formation can be carried out by metal plating or the like.

[0034] Furthermore, the laminated substrate of this embodiment can also be a conductive laminated substrate. For example, it can be a laminated substrate comprising an insulating layer made of a prepreg containing the resin composition for low dielectric material and a conductive layer. The insulating prepreg is formed by impregnating a fibrous substrate such as glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, or glass roving cloth with the resin composition for low dielectric material to form the insulating layer. The conductive layer can be made of a metal, such as copper.

[0035] Furthermore, the laminated substrate of this embodiment can also be a build-up printed circuit board type laminated substrate. A build-up printed circuit board type laminated substrate can also be formed by alternately forming an insulating layer made of a resin composition for low dielectric material and a conductive layer plated thereon on a wiring board. The composition and other configurations of the insulating layer and conductive layer can be arbitrarily selected from those described above.

[0036] (Other configurations) The resin composition for low dielectric materials of this embodiment can be used by appropriately mixing in components conventionally known as materials for low dielectric materials. As mentioned above, the resin composition for low dielectric materials in this embodiment has high affinity with epoxy resins, bismaleimide resins, or cyanate resins, and therefore, by mixing it with thermosetting resin-based materials, it can be expected to improve dielectric and thermal properties.

[0037] (Effects of resin compositions for low dielectric materials) The resin composition for low dielectric materials of this embodiment is suitable for use as a low dielectric material because the triazine-containing polyether has a low dielectric constant, low dielectric loss tangent, high transparency, high solubility, and high heat resistance. Furthermore, the triazine-containing polyether of this embodiment is suitable for use as a printed circuit board because it has a low dielectric constant, low dielectric loss tangent, high transparency, high solubility, and high heat resistance. While very few conventionally known polymer materials achieve both a glass transition temperature of over 260°C and a dielectric loss tangent of less than 0.002, these can be achieved within the preferred range of this embodiment. Furthermore, the triazine-containing polyether of this embodiment is particularly suitable for use as a constituent material for high-frequency electronic components and electronic devices because it has a low dielectric constant at high frequencies, a low dielectric loss tangent, high transparency, high solubility, and high heat resistance.

[0038] (Method for manufacturing resin compositions for low dielectric materials) The method for producing the resin composition for low dielectric materials of this embodiment involves mixing a compound represented by the following general formula (16) and a compound represented by the following general formula (17), and polymerizing them to obtain a triazine-containing polyether compound represented by the following general formula (18).

[0039] [ka] [ka] [ka]

[0040] Here, in formula (18), n is an integer greater than or equal to 2, and Ar is an arylene group, representing a divalent aromatic group with or without substituents. In the formula, n represents the number of repeating units of the structure represented by formula (18), and is not particularly limited as long as it is an integer of 2 or more. Examples of substituents include those having 1 to 18 carbon atoms. Preferred substituents include alkyl groups such as methyl, alkylene groups such as methylene, alkylidene groups such as isopropylidene, cycloalkyl groups such as cyclohexyl, cycloalkylene groups such as cyclohexylene, cycloalkylidene groups such as cyclohexylidene, aryl groups such as phenyl, arylene groups such as phenylene, fluorinated alkyl groups such as trifluoromethyl, fluorinated alkylene groups such as perfluorohexylene, fluorinated aryl groups such as trifluoromethylphenyl, and fluorinated arylene groups such as trifluoromethylphenyl. R is an organic substituent, which may be hydrogen, or a linear, branched, or cyclic aliphatic group. R may also be an aromatic group with or without substituents. In addition, R may be any of the aforementioned fluorinated aliphatic groups or any of the aforementioned fluorinated aromatic groups. Examples of organic substituents include those having 1 to 18 carbon atoms. Preferred organic substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, dimethylphenyl, cumenyl, mesityl, tert-butylphenyl, naphthyl, trifluoromethyl, trifluoromethylphenyl, bistrifluoromethylphenyl, trifluoromethylphenoxy, or bistrifluoromethylphenoxy.

[0041] The specific manufacturing process involves, for example, mixing the compounds of formula (16) and formula (17), and polymerizing them by heating them in a polar solvent in the presence of an alkali metal compound to obtain the compound of formula (18).

[0042] Any alkali metal compound can be used as the alkali metal compound, as long as it is possible to substitute the compound of formula (17) with an alkali metal salt. Examples of such alkali metal compounds include alkali metal carbonates, bicarbonates, or hydroxides, with carbonates being particularly preferred. Examples of the alkali metal include lithium, sodium, potassium, rubidium, or cesium, with sodium or potassium being preferred. Such alkali metal compounds can include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, or potassium hydroxide, with potassium carbonate or cesium carbonate being particularly suitable. These alkali metal compounds may be used individually or in combination of two or more.

[0043] The polar solvent can be any one that can facilitate the polymerization reaction. Specific examples of polar solvents include, for example, 1,3-dimethyl-2-imidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide (DMSO), sulfolane (SUL), and diphenylsulfone. Of these, DMI or NMP is preferred. These various polar solvents may be used individually or in combination of two or more. They can also be used as mixed solvents with other solvents (for example, aromatic solvents such as toluene).

[0044] Furthermore, at an appropriate point during the reaction using the aforementioned polar solvent, an appropriate amount of an inert solvent component, such as toluene or xylene, may be added. By adding these solvents, which readily form azeotropes with water, the water generated by the reaction can be efficiently removed from the reaction system.

[0045] The polymerization temperature can be adjusted as appropriate depending on the compound, additives, and solvent used, but it is generally preferable to carry it out at 140-300°C, and more preferably at 180-250°C. Below this temperature range, sufficient reaction rate and degree of polymerization cannot be obtained, making it inefficient. Furthermore, exceeding this temperature range may cause the resulting compound to decompose or deteriorate. The polymerization reaction time can be adjusted as appropriate depending on the components used and the polymerization temperature, but it is usually around 0.1 to 20 hours. For example, when NMP or DMI is used as the polar solvent, polymerization proceeds sufficiently in 3 to 4 hours at a polymerization temperature of 190 to 200°C. To increase the molecular weight, it is preferable to polymerize for 15 to 20 hours, or to use the point when polymerization has sufficiently progressed, such as when the stirring bar stops, as an indicator of completion.

[0046] As an example of a specific manufacturing process, first, an inert solvent component is added to the compounds of formulas (16) and (17), an alkali metal compound, and a polar solvent, and heated, gradually raising the polymerization temperature from room temperature to 140-150°C. While maintaining that temperature, the inert solvent component and water are removed by azeotrope. Next, the temperature is raised to the polymerization temperature, and while maintaining that temperature, the inert solvent component is completely removed. After the inert solvent component has been removed, the polymerization temperature is maintained, and polymerization is carried out for the aforementioned polymerization reaction time to obtain the compound of formula (18). After the polymerization reaction is fully completed, it is allowed to cool to room temperature and recovered with methanol. After this, further steps such as washing with methanol, drying under reduced pressure, and / or reprecipitation with an organic solvent may be performed.

[0047] (Other additives in the manufacturing process) When the resin composition for low dielectric materials of this embodiment is a resin composition for low dielectric materials used as an insulating material between layers of a laminated substrate, it is preferable that this resin composition for low dielectric materials is manufactured by mixing a triazine-containing polyether compound, an epoxy resin, a bismaleimide resin, or a cyanate resin, a curing accelerator, and an organic solvent. By manufacturing the resin composition for low dielectric materials with a curing accelerator, the curing reaction proceeds rapidly, making it easy to manufacture as an insulating material. In particular, when the insulating material is used as an insulating layer on the surface of a laminated substrate film, as described later, the insulating layer is formed quickly, making it suitable for industrial manufacturing. By being manufactured by mixing with organic solvents, the resin composition for low dielectric materials becomes a so-called varnish during manufacturing, making it easy to apply to other components as an insulating material. In particular, when the insulating material is used as an insulating layer on the surface of a laminated substrate film, as described later, the coating properties are good when applying it to the surface of the film to form an insulating layer.

[0048] As a curing accelerator, any compound capable of accelerating the curing of the aforementioned compound can be used as appropriate, for example, imidazoles, tertiary amines, acid anhydrides, or tertiary phosphines may be used. The amount added can be appropriately adjusted depending on the composition of the compound, but it is preferably in the range of 0.01 to 2% by mass relative to the total mass of the resin composition for low dielectric materials.

[0049] As the organic solvent, any solvent capable of dissolving the compound and forming a varnish can be appropriately selected. For example, known organic solvents such as alcoholic solvents, ketones, acetate esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone can be used. Among these, propylene glycol monomethyl ether acetate, cyclohexanone, or methyl ethyl ketone can be suitably used. The amount added can be appropriately adjusted depending on the composition of the compound, but to achieve a varnish-like consistency, it is preferable that the non-volatile content be in the range of 50 to 70% by mass relative to the total mass of the resin composition for low dielectric materials.

[0050] The resin composition for low dielectric materials in this embodiment may also be manufactured by further mixing in an inorganic filler, a modifier, or a flame retardant. Inorganic fillers can include, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, or magnesium hydroxide. When resin compositions for low dielectric materials are used in applications such as conductive pastes and conductive films, conductive fillers such as silver powder or copper powder can be used as inorganic fillers. Examples of modifiers that can be used include phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, or polyethylene terephthalate resin. For example, the flame retardant can be a halogen compound, a phosphorus-containing compound, a nitrogen-containing compound, or an inorganic flame retardant.

[0051] (Method of manufacturing film for laminated substrates) The method for manufacturing a laminated substrate film according to this embodiment involves applying an insulating material containing a resin composition for low dielectric materials to at least one surface of a resin film. Specifically, the above manufacturing method involves applying a varnish-like resin composition for low dielectric materials, as described above, to at least one surface of a resin film. Then, the organic solvent is evaporated by heating or blowing hot air to form an insulating layer, thereby enabling the manufacturing process.

[0052] Here, it is preferable that the resin composition for the low dielectric material has a non-volatile content of 30 to 60% by mass, excluding volatile components such as organic solvents. This range is particularly favorable for the coating properties of the compound onto films and for the moldability of films for laminated substrates.

[0053] The thickness of the insulating layer formed is preferably greater than or equal to the thickness of the conductive layer of the circuit board on which the laminated substrate is installed, as will be described later. If the thickness of the conductive layer of the circuit board is usually in the range of 5 to 70 μm, then the thickness of the resin composition layer is preferably 10 to 100 μm.

[0054] (Method of manufacturing a laminated substrate) The manufacturing method of the laminated substrate of this embodiment involves stacking two or more of the aforementioned films for the laminated substrate. When manufacturing a printed circuit board using the laminated substrate of this embodiment, if the film for the laminated substrate is protected by a protective film, these can be removed, and then the layer can be laminated to one or both sides of the circuit board so that it is in direct contact with the circuit board, for example by vacuum lamination. The lamination method may be batch or continuous with a roll. The film and circuit board may also be heated (preheated) before lamination as necessary.

[0055] When manufacturing a conductive laminated substrate, it may be formed by the following procedure. That is, the resin composition for low dielectric material, which has been adjusted to a varnish-like state as described above, is impregnated into a fibrous substrate, and an insulating layer of prepreg, which is a cured product, is obtained by heating at a heating temperature corresponding to the type of solvent used, preferably 50 to 170°C. The fibrous substrate can be paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, matted glass, or glass roving cloth. In this case, it is generally preferable to adjust the mixing ratio of the resin composition for low dielectric material and the fibrous substrate so that the resin content in the prepreg is 20 to 60% by mass. The obtained prepregs are laminated, and a film of a material that will become a conductive layer, such as copper foil, is then layered on top and heated and pressed to obtain the desired conductive plate laminate substrate. Specifically, the heating and pressing method is performed under pressure of 1 to 10 MPa at a temperature of 170 to 250°C. Furthermore, it is preferable to perform the heating and pressing for 10 minutes to 3 hours.

[0056] When using a film for laminated substrates as a build-up printed circuit board, the laminated substrate and printed circuit board may be formed by the following procedure. Specifically, a resin composition for low dielectric material is applied to a wiring board with a circuit formed on it using a spray coating method or a curtain coating method, and then cured. Next, holes such as predetermined through-holes are drilled as needed, then the surface is treated with a roughening agent and washed with hot water to form irregularities, and then plated with a metal such as copper. The plating method is preferably electroless plating or electrolytic plating. As the roughening agent, an oxidizing agent, alkali, or organic solvent can be used. By sequentially repeating these operations as desired, an insulating layer and a conductor layer of a predetermined circuit pattern are alternately built up to form a build-up substrate. However, it is preferable to drill through-holes after forming the outermost insulating layer. Furthermore, it is possible to create a roughened surface and omit the plating process by heating and pressing the resin-coated copper foil, which has been partially cured with the resin composition on copper foil, onto a wiring board with a circuit formed on it at 170-250°C, thereby producing a build-up substrate.

[0057] (Method of manufacturing encapsulating materials for electronic components, etc.) To prepare the resin composition for low dielectric materials of this embodiment as an encapsulant for electronic components, one method involves pre-mixing the resin composition for low dielectric materials, epoxy resin, bismaleimide resin, or cyanate resin, other coupling agents and / or release agents as needed, and other additives and inorganic fillers, and then thoroughly mixing them using an extruder, kneader, rolls, etc., until homogeneous. When used as a tape-shaped encapsulant for semiconductors, one method involves heating the resin composition obtained by the above method to produce a semi-cured sheet, forming an encapsulant tape, placing this encapsulant tape on a semiconductor chip, heating it to 100-150°C to soften and mold it, and then completely curing it at 170-250°C.

[0058] To prepare the resin composition for low dielectric materials of this embodiment as a resist ink, one method is to add the resin composition for low dielectric materials, epoxy resin, bismaleimide resin, or cyanate resin, as well as an organic solvent, pigment, talc, and filler, to form a resist ink composition, then apply it to a printed circuit board using a screen printing method, and finally cure the resist ink. Examples of organic solvents used here include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, cyclohexanone, dimethyl sulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, or ethyl lactate.

[0059] When the resin composition for low dielectric materials of this embodiment is used as an insulating material, for example, as an insulating material between layers of a semiconductor, one method is to prepare the composition by blending the resin composition for low dielectric materials, epoxy resin, bismaleimide resin, or cyanate resin with a curing accelerator and a silane coupling agent, and then applying this to a silicon substrate by spin coating or the like. In this case, since the cured coating film will be in direct contact with the semiconductor, it is preferable to bring the coefficient of thermal expansion of the insulating material close to that of the semiconductor so that cracks do not occur due to differences in coefficient of thermal expansion in high-temperature environments.

[0060] When the resin composition for low dielectric materials of this embodiment is used as a conductive paste, examples include dispersing fine conductive particles in the resin composition for low dielectric materials to create a composition for an anisotropic conductive film, or creating a paste resin composition for circuit connection or an anisotropic conductive adhesive that is liquid at room temperature. [Examples]

[0061] Examples are shown below. However, the present invention is not limited to these examples.

[0062] (Test conditions) The following instruments and reagents were used for the synthesis of the samples and the analysis of the synthesized samples. The equipment and conditions used are as follows: (1) GPC: Tosoh Corporation high-speed GPC system HLC-8220GPC (Column: Tosoh TSKgel (α-M), Column temperature: 45℃, Eluent: N-methyl-2-pyrrolidone (NMP) (containing 0.01 mol / L lithium bromide), or tetrahydrofuran (THF), Calibration curve: Standard polystyrene, Column flow rate: 0.2 mL / min) (2) Infrared spectrum (FT-IR): FT / IR-4200 manufactured by JASCO Corporation (3) Nuclear magnetic resonance (NMR) spectrum: JEOL Ltd. JNM-ECA500 (4) Thermogravimetric analysis (TGA): Hitachi High-Tech Science Corporation TG / DTA7220, heating rate 10°C / min (5) Differential scanning calorimetry (DSC): Hitachi High-Tech Science Corporation DSC7000, heating rate 20°C / min (6) Thermomechanical analysis (TMA): Hitachi High-Tech Science Co., Ltd. TMA7100, heating rate 10°C / min (7) Dynamic viscoelasticity measurement (DMA): Hitachi High-Tech Science Co., Ltd. DMS7100, heating rate 2°C / min (8) Tensile test: Shimadzu Corporation Autograph AGS-D type, tensile speed 1 mm / min (9) Ultraviolet-Visible Spectrum: Shimadzu Corporation UV-1800 (10) Refractive index measurement: Metricon Model 2010 / M PRISM COUPLER (11) Dielectric constant measurement: Dielectric constant / dielectric loss tangent measuring device (cavity resonator type) manufactured by AET Co., Ltd., TM mode (10 GHz), TE mode (10 GHz) The reagents used were commercially available and purified by conventional methods as needed. The various reaction solvents were dried and purified by conventional methods as needed.

[0063] (Manufacturing of resin compositions) Among the compounds of formula (1) above, R = hydrogen (H) (BFPT), and Ar is, Compound of BisA according to formula (2) (BFPT-BisA, Example 1) Compound of BisAF in formula (3) (BFPT-BisAF, Example 2) Compound of BisPHTG of formula (4) (BFPT-BisPHTG, Example 3) Compound of BisPIND according to formula (5) (BFPT-BisPIND, Example 4) Compound of BisC according to formula (6) (BFPT-BisC, Example 5) Compound of TMBisA of formula (7) (BFPT-TMBisA, Example 6) Compound of BisCHP according to formula (8) (BFPT-BisCHP, Example 7) A compound of BisZ from formula (9) and BisAF from formula (3) (BFPT-BisZ / BisAF, Example 8) Compound of BisP3MZ of formula (10) and BisAF of formula (3) (BFPT-BisP3MZ / BisAF, Example 9) Compound of BisPCDE of formula (11) (BFPT-BisPCDE, Example 10) Compound of DTPM of formula (12) (BFPT-DTPM, Example 11) Compound of BPFL of formula (13) (BFPT-BPFL, Example 12) Compound of DMBPFL of formula (14) (BFPT-DMBPFL, Example 13) Compound of TBISRX of formula (15) (BFPT-TBISRX, Example 14) I made adjustments.

[0064] For the compounds of formula (16) and formula (17) used in the manufacturing process, the compound of formula (16) was a compound (BFPT) in which R = hydrogen (H). For the compound of formula (17), in each example, the compounds of formula (2) (Example 1), formula (3) (Example 2), formula (4) (Example 3), formula (5) (Example 4), formula (6) (Example 5), formula (7) (Example 6), formula (8) (Example 7), formula (9) (Example 8), formula (10) (Example 9), formula (11) (Example 10), formula (12) (Example 11), formula (13) (Example 12), formula (14) (Example 13), and formula (15) (Example 14) were used, with Ar being the compound of formula (15) (Example 14).

[0065] (Synthesis of 2,4-bis(4-fluorophenyl)-2-phenyl-1,3,5-triazine (BFPT)) The BFPT used in each example was synthesized as follows. In a three-necked flask (100 mL) equipped with a stirring bar and a nitrogen gas inlet tube, 7.460 g of 4-fluorobenzamidine hydrochloride, 42.73 mmol of benzylideneaniline, 3.625 g of benzylideneaniline, 3.781 g of sodium bicarbonate, and 35 mL of N,N-dimethylformamide (DMF) were added. The temperature was gradually increased to 85°C, and the mixture was reacted at 85°C for 96 hours. After cooling to room temperature, the mixture was added to distilled water and chloroform was added. The chloroform solution was washed three times with distilled water using a separatory funnel. The recovered chloroform solution was dried overnight over anhydrous sodium sulfate, and after removing the anhydrous sodium sulfate by suction filtration, the chloroform solution was concentrated using an evaporator and added to methanol (500 mL), at which point the crude product precipitated. This was collected by suction filtration, washed with methanol under reflux, and then dried under reduced pressure at room temperature to obtain a crude product (1.61 g, 23.3%) in the form of brown needle-shaped crystals. The crude product was recrystallized in a mixed solvent of chloroform and methanol and dried under reduced pressure at 80°C for 24 hours.

[0066] The synthesized compound had the following characteristics: shape: white needle-shaped crystals, yield: 1.46 g, yield: 21.1%, melting point: 258-259°C. Regarding this BFPT, the analysis results using the aforementioned equipment are: FT-IR (KBr, cm) -1 ):3051(Ar-H),1603 (C=C),1522 (C=N),1508(C=C),1370 (CN),1228 (Ar-F) 1 H-NMR (CDCl3, ppm):8.78-8.73 (m,6H),7.61 (t,1H),7.57 (t,2H),7.26-7.23 (m,4H) 13C-NMR (CDCl3, ppm): 171.74,170.75,165.93,136.06,132.78,132.35,131.38,128.89,115.83 19 F-NMR (CDCl3, ppm): 108.41 Elemental analysis (C 21 H 13 F2N3): Calculated values ​​were C, 73.03%; H, 3.79%; N, 12.17%. Measured values ​​were C, 73.02%; H, 3.89%; N, 12.40%.

[0067] (Example 1) The compound of Example 1, the polyether (BFPT-BisA) shown below, was synthesized as follows. [ka] In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and bisphenol A (0.4566 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water using the Dean-Stark trap. The temperature was then increased to 190°C and stirred for 1 hour to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a viscous polymerization solution was obtained. The polymer was precipitated by pouring it into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature for 12 hours. The obtained polymer was dissolved in NMP, poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature for 12 hours.

[0068] The yield was 0.761 g, the yield rate was 71%, the logarithmic viscosity was 1.12 dL / g (30°C, 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC (NMP) was 75,000, the weight-average molecular weight (Mw) was 133,000, the molecular weight distribution (Mw / Mn) was 1.8, and the average degree of polymerization (n) was 140.

[0069] This polymer was dissolved in NMP to prepare a 12 wt% solution. This solution was cast onto a glass plate and gradually heated to 160°C under reduced pressure, then dried under reduced pressure at 160°C for 1 hour. The glass plate was immersed in distilled water to remove the film, and dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 38 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3066(Ar-H),2968(CH),1592(C=C),1517(C=N),1504(C=C),1368(CN),1241(Ar-O). 1 H-NMR (CDCl3, ppm):8.68(d,6H),7.53-7.50(m,3H),7.24(d,4H),7.09(d,4H),7.00(d,4H),1.69(s,6H) Elemental analysis (C 36 H 27 O2N3) n Calculated values: C, 81.02%; H, 5.10%; N, 7.88% Measured values: C, 80.72%; H, 5.17%; N, 7.88% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), and N,N'-dimethylimidazolidone (DMI). Glass transition temperature (Tg): 245°C (DSC), 239°C (DMA), 250°C (TMA) Coefficient of thermal expansion (CTE): 87 ppm / °C (in the range of 150 to 200°C) 5% weight loss temperature (T 5% ): 448℃ (in air), 525℃ (in nitrogen) 10% weight loss temperature (T 10%): 486℃ (in air), 534℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 40% Cutoff wavelength: 353nm Transmittance (500nm): 81% Average refractive index (n ave ):1.675(d line) Birefringence (Δn): 0.015 (d line) Permittivity (ε=n ave 2 ):2.81 Dielectric constant (Dk): 2.78 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.58 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0026 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0024 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 61 MPa Elongation at break: 21.9% Initial tensile modulus: 1.8 GPa That was the case.

[0070] (Example 2) The compound of Example 2, the polyether (BFPT-BisAF) shown below, was synthesized as follows. [ka] In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and bisphenol AF (0.6725 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N,N'-dimethylimidazolidone (DMI, 6.5 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water using the Dean-Stark trap. The temperature was then increased to 190°C and stirred for 1 hour to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a viscous polymerization solution was obtained. The polymer was poured into methanol to precipitate, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in tetramethylurea (TMU), poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0071] The yield was 1.021 g, the yield rate was 80%, the logarithmic viscosity was 0.98 dL / g (at 30°C in a 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 106,000, the weight-average molecular weight (Mw) was 211,000, the molecular weight distribution (Mw / Mn) was 2.0, and the average degree of polymerization (n) was 165.

[0072] The polymer was dissolved in TMU to prepare a 9 wt% solution. This solution was cast onto a glass plate and gradually heated to 160°C under reduced pressure, followed by vacuum drying at 160°C for 1 hour. The glass plate was immersed in distilled water to remove the film, and then vacuum dried at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 37 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3064(Ar-H),1595(C=C),1518(C=N),1506(C=C),1368(CN),1248(Ar-O) 1H-NMR (CDCl3, ppm):8.74-8.69(m,6H),7.55-7.49(m,3H),7.42(d,4H),7.17(d,4H),7.07(d,4H) Elemental analysis (C 36 H 21 N3O2F6) n Calculated values: C, 67.40%; H, 3.29%; N, 6.55% Measured values: C, 67.37%; H, 3.48%; N, 6.70% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), N,N-dimethylacetamide (DMAc), cyclohexanone, cyclopentanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 248°C (DSC), 249°C (DMA), 280°C (TMA) Coefficient of thermal expansion (CTE): 72 ppm / °C (range of 150 to 200°C) 5% weight loss temperature (T 5% ): 526℃ (in air), 534℃ (in nitrogen) 10% weight loss temperature (T 10% ): 545℃ (in air), 548℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 62% Cutoff wavelength: 343nm Transmittance (500nm): 83% Average refractive index (n ave ):1.621(d line) Birefringence (Δn): 0.021 (d line) Permittivity (ε=n ave 2 ):2.63 Dielectric constant (Dk): 2.65 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.56 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0016 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0015 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 63 MPa Elongation at break: 6.1% Initial tensile modulus: 2.1 GPa That was the case.

[0073] (Example 3) The compound of Example 3, the polyether (BFPT-BisPHTG) shown below, was synthesized as follows. [ka] In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and BisP-HTG (0.6209 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water using the Dean-Stark trap. The temperature was then increased to 190°C and stirred for 1 hour to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was precipitated by pouring it into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in NMP and poured into methanol, allowing the white, flaky polymer to precipitate. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0074] The yield was 1.163 g, the yield rate was 94%, the logarithmic viscosity was 0.48 dL / g (30°C, 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 38,000, the weight-average molecular weight (Mw) was 65,000, the molecular weight distribution (Mw / Mn) was 1.7, and the average degree of polymerization (n) was 61.

[0075] The polymer was dissolved in TMU to prepare a 15 wt% solution. This solution was cast onto a glass plate and gradually heated to 160°C under reduced pressure, followed by vacuum drying at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and then vacuum dried at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 38 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),2948(CH),1593(C=C),1518(C=N),1504(C=C),1368(CN),1242(Ar-O) 1 H-NMR (CDCl3, ppm):8.68-8.50(m,6H),7.52-7.48(m,3H),7.36(d,2H),7.23(d,2H),7.05(d,4H),7.00(d,2H),6.94(d,2H), 2.71(d,1H),2.47(d,1H),2.04-2.01(br,1H),1.96(d,1H),1.41(d,1H),1.20(t,1H),1.00(s,6H),0.89(t,1H),0.43(s,3H) Elemental analysis (C 42 H 37 N3O2) n Calculated values: C, 81.92%; H, 6.06%; N, 6.82% Measured values: C, 81.88%; H, 6.18%; N, 6.88% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), N,N'-dimethylpropyleneurea (DMPU), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 279°C (DSC), 277°C (DMA), 281°C (TMA) Coefficient of thermal expansion (CTE): 75 ppm / °C (range of 150 to 200°C) 5% weight loss temperature (T 5% ): 480℃ (in air), 511℃ (in nitrogen) 10% weight loss temperature (T 10%): 496℃ (in air), 520℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 25% Cutoff wavelength: 354nm Transmittance (500nm): 81% Average refractive index (n ave ):1.637(d line) Birefringence (Δn): 0.006 (d line) Permittivity (ε=n ave 2 ):2.68 Dielectric constant (Dk): 2.64 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.57 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0018 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0014 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 73 MPa Elongation at break: 4.5% Initial tensile modulus: 2.0 GPa That was the case.

[0076] (Example 4) The compound of Example 4, the polyether (BFPT-BisPIND) shown below, was synthesized as follows. [ka] In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and BisPIND (0.5368 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water using the Dean-Stark trap. The temperature was then increased to 190°C and stirred for 1 hour to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was precipitated by pouring it into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in NMP, poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0077] The yield was 1.030 g, the yield rate was 90%, the logarithmic viscosity was 0.96 dL / g (at 30°C in a 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 112,000, the weight-average molecular weight (Mw) was 380,000, the molecular weight distribution (Mw / Mn) was 3.4, and the average degree of polymerization (n) was 195.

[0078] The polymer was dissolved in TMU to prepare a 10 wt% solution. This solution was cast onto a glass plate and gradually heated to 160°C under reduced pressure, followed by vacuum drying at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and then vacuum dried at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 43 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),2958(CH),1593(C=C),1518(C=N),1507(C=C),1368(CN),1239(Ar-O) 1H-NMR (CDCl3, ppm):8.63-8.58(m,6H),7.46-7.42(m,3H),7.19-7.17(m,3H),7.07-7.04(m,2H), 7.00-6.96(m,5H),6.86(s,1H),2.43(d,1H),2.24(d,1H),1.67(s,3H),1.36(s,3H),1.11(s,3H) Elemental analysis (C 39 H 31 N3O2) n Calculated values: C, 81.65%; H, 5.45%; N, 7.32% Measured values: C, 81.41%; H, 5.56%; N, 7.23% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), N,N'-dimethylpropyleneurea (DMPU), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 266°C (DSC), 265°C (DMA), 286°C (TMA) Coefficient of thermal expansion (CTE): 78 ppm / °C (range of 150 to 200°C) 5% weight loss temperature (T 5% ): 512℃ (in air), 513℃ (in nitrogen) 10% weight loss temperature (T 10% ): 522℃ (in air), 520℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 30% Cutoff wavelength: 352nm Transmittance (500nm): 84% Average refractive index (n ave ):1.653(d line) Birefringence (Δn): 0.012 (d line) Permittivity (ε=n ave 2 ):2.73 Dielectric constant (Dk): 2.71 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.72 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0020 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0018 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 63 MPa Elongation at break: 3.6% Initial tensile modulus: 1.9 GPa That was the case.

[0079] (Example 5) The compound of Example 5, the polyether (BFPT-BisC) shown below, was synthesized as follows. [ka] In Example 1, BisA was replaced with BisC, and polymerization was carried out in NMP (5.0 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.

[0080] The yield was 1.07 g, the yield rate was 95%, the logarithmic viscosity was 0.67 dL / g (30°C, 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 55,000, the weight-average molecular weight (Mw) was 109,000, the molecular weight distribution (Mw / Mn) was 2.0, and the average degree of polymerization (n) was 97.

[0081] The polymer was dissolved in NMP, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 47 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),2968(CH),1593(C=C),1518(C=N),1501(C=C),1368(CN),1239(Ar-O) 1 H-NMR (CDCl3, ppm):8.70-8.68(m,6H),7.55-7.49(m,3H),7.18(br,2H),7.10(d,2H),7.02(d,4H),6.94(d,2H),2.20(s,6H),1.71(s,6H) Elemental analysis (C 38 H 31 N3O2) n Calculated values: C, 81.26%; H, 5.56%; N, 7.48% Measured values: C, 81.67%; H, 5.72%; N, 7.50% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 229°C (DSC), 228°C (DMA), 267°C (TMA) Coefficient of thermal expansion (CTE): 91 ppm / °C (in the range of 150 to 200°C) 5% weight loss temperature (T 5% ): 450℃ (in air), 468℃ (in nitrogen) 10% weight loss temperature (T 10% ): 478℃ (in air), 472℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 28% Cutoff wavelength: 352nm Transmittance (500nm): 78% Average refractive index (n ave ):1.663(d line) Birefringence (Δn): 0.014 (d line) Permittivity (ε=n ave 2 ):2.77 Dielectric constant (Dk): 2.75 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.71 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0011 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0010 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 77 MPa Elongation at break: 11.2% Initial tensile modulus: 2.0 GPa That was the case.

[0082] (Example 6) The compound of Example 6, the polyether (BFPT-TMBisA) shown below, was synthesized as follows. [ka] In Example 1, BisA was replaced with TMBisA, and polymerization was carried out in NMP (5 mL) at 200°C for 3 hours to synthesize a polyether in the same manner.

[0083] The yield was 1.12 g, the yield rate was 95%, the logarithmic viscosity was 0.43 dL / g (at 30°C in a 0.5 g / dL NMP solution), and the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 43,000, the weight-average molecular weight (Mw) was 77,000, the molecular weight distribution (Mw / Mn) was 1.8, and the average degree of polymerization (n) was 72.

[0084] The polymer was dissolved in NMP, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 63 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3064(Ar-H),2968(CH),1606(C=C),1521(C=N),1510(C=C),1368(CN),1235(Ar-O) Elemental analysis (C 40 H 35 N3O2) n Calculated values: C, 81.46%; H, 5.98%; N, 7.13% Measured values: C, 81.54%; H, 6.10%; N, 7.02% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 286°C (DSC), 285°C (DMA), 308°C (TMA) Coefficient of thermal expansion (CTE): 74 ppm / °C (range of 150 to 200°C) 5% weight loss temperature (T 5% ): 419 °C (in air), 450 °C (in nitrogen) 10% weight loss temperature (T 10% ): 442 °C (in air), 453 °C (in nitrogen) Carbonization yield (in nitrogen, 800 °C): 22% Cut-off wavelength: 348 nm Transmittance (500 nm): 78% Average refractive index (n ave ): 1.634 (d line) Birefringence (Δn): 0.017 (d line) Dielectric constant (ε = n ave 2 ): 2.67 Dielectric constant (Dk): 2.66 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.62 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0014 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0016 (cavity resonator, TE mode, 10 GHz) Tensile break strength: 61 MPa Elongation at break: 3.5% Initial tensile modulus: 2.0 GPa was.

[0085] (Example 7) The compound of Example 7, the polyether (BFPT-BisCHP) of the following formula, was synthesized as follows. [Chemical formula] BisA of Example 1 was changed to BisCHP, and polymerization was carried out at 190 °C for 3 hours in NMP (5 mL) to synthesize polyether in the same manner.

[0086] <00009Yield: 1.33 g, yield rate: 95%, logarithmic viscosity: 0.57 dL / g (in a 0.5 g / dL NMP solution at 30°C), number average molecular weight (Mn) measured by the aforementioned GPC (THF): 56,000, weight average molecular weight (Mw): 119,000, molecular weight distribution (Mw / Mn): 2.1, average degree of polymerization (n): 80.

[0087] The polymer was dissolved in NMP, cast onto a glass plate, and the temperature was gradually raised to 160°C under reduced pressure and dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to peel off the film, and dried under reduced pressure at 200°C for 3 hours to prepare a colorless and transparent cast film (film thickness 53 μm). Regarding this example, the analysis results using the aforementioned equipment are FT-IR (film, cm -1 ): 3066 (Ar-H), 2926 (C-H), 1588 (C=C), 1521 (C=N), 1519 (C=C), 1368 (C-N), 1234 (Ar-O) Elemental analysis (C 48 H 47 N3O2) n : Calculated value C, 82.60%; H, 6.79%; N, 6.02%. Measured value C, 82.67%; H, 6.85%; N, 6.03% Solubility: Soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), chloroform. Glass transition temperature (Tg): 221°C (DSC), 221°C (DMA), 222°C (TMA) Coefficient of thermal expansion (CTE): 95 ppm / °C (in the range of 150 to 200°C) 5% weight loss temperature (T 5% ): 455°C (in air), 469°C (in nitrogen) 10% weight loss temperature (T 10% ): 465°C (in air), 472°C (in nitrogen) Char yield (in nitrogen, 800°C): 9% Cut-off wavelength: 350 nm Transmittance (500 nm): 80% Average refractive index (n ave): 1.630 (d line) Birefringence (Δn): 0.007 (d line) Dielectric constant (ε = n ave 2 ): 2.66 Dielectric constant (Dk): 2.62 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.64 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0008 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0009 (cavity resonator, TE mode, 10 GHz) Tensile break strength: 75 MPa Elongation at break: 4.1% Initial tensile modulus: 2.3 GPa was as follows.

[0088] (Example 8) The compound of Example 8, the polyether of the following formula [BFPT - BisZ / BisAF (25 mol% / 75 mol%)] was synthesized as follows. [Chemical formula] BisA in Example 1 was changed to BisZ (25 mol%) and BisAF (75 mol%), and polymerization was carried out at 190 °C for 3 hours in NMP (5 mL), and polyether was synthesized in the same manner.

[0089] Yield: 94%, logarithmic viscosity: 1.06 dL / g (30 °C, 0.5 g / dL NMP solution), number average molecular weight (Mn) measured by the aforementioned GPC (THF): 80,000, weight average molecular weight (Mw): 192,000, molecular weight distribution (Mw / Mn): 2.4, average degree of polymerization (n): 128.

[0090] The polymer was dissolved in NMP, cast on a glass plate, and the temperature was gradually raised to 160 °C under reduced pressure and dried under reduced pressure at 160 °C for 3 hours. The glass plate was immersed in distilled water to peel off the film, and dried under reduced pressure at 200 °C for 3 hours to prepare a colorless transparent cast film (film thickness 84 μm). For this example, the analysis results using the aforementioned equipment are FT-IR (film, cm -1 ): 3068 (Ar-H), 2936 (C-H), 1596 (C=C), 1521 (C=N), 1502 (C=C), 1368 (C-N), 1246 (Ar-O) Elemental analysis (C 36.75 H 23.5 N3O2F 4.5 ) n : Calculated value C, 70.67%; H, 3.79%; N, 6.73%. Measured value C, 71.08%; H, 3.97%; N, 6.67% Solubility: Soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidinone (DMI), N,N'-dimethylpropyleneurea (DMPU), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), chloroform. Glass transition temperature (Tg): 250 °C (DSC), 248 °C (DMA) Coefficient of thermal expansion (CTE): 83 ppm / °C (range from 150 to 200 °C) 5% weight loss temperature (T 5% ): 517 °C (in air), 514 °C (in nitrogen) 10% weight loss temperature (T 10% ): 536 °C (in air), 528 °C (in nitrogen) Carbonization yield (in nitrogen, 800 °C): 59% Cutoff wavelength: 351 nm Transmittance (500 nm): 79% Average refractive index (n ave ): 1.634 (d line) Birefringence (Δn): 0.022 (d line) Dielectric constant (ε = n ave 2 ): 2.67 Dielectric constant (Dk): 2.77 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.76 (cavity resonator, TE mode, 10 GHz) Dielectric tangent (Df): 0.0017 (cavity resonator, TM mode, 10 GHz) Dielectric tangent (Df): 0.0016 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 73 MPa Elongation at break: 5.6% Initial tensile modulus: 2.1 GPa That was the case.

[0091] (Example 9) The compound of Example 9, the polyether [BFPT-BisP3MZ / BisAF(50 mol% / 50 mol%)], was synthesized as follows. [ka] In Example 1, BisA was replaced with BisP3MZ (50 mol%) and BisAF (50 mol%), and polymerization was carried out in NMP (5 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.

[0092] The yield was 1.030 g, the yield rate was 84%, the logarithmic viscosity was 0.81 dL / g (at 30°C in a 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 47,000, the weight-average molecular weight (Mw) was 110,000, the molecular weight distribution (Mw / Mn) was 2.1, and the average degree of polymerization (n) was 76.

[0093] The polymer was dissolved in NMP, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 58 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3064(Ar-H),2929(CH),1594(C=C),1518(C=N),1506(C=C),1368(CN),1246(Ar-O) Elemental analysis (C 38 H 27 N3O2F3) n Calculated values: C, 74.25%; H, 4.43%; N, 6.84% Measured values: C, 74.34%; H, 4.57%; N, 6.83% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), N,N'-dimethylpropyleneurea (DMPU), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 260°C (DSC), 259°C (DMA) Coefficient of thermal expansion (CTE): 78 ppm / °C (range of 150 to 200°C) 5% weight loss temperature (T 5% ): 499℃ (in air), 510℃ (in nitrogen) 10% weight loss temperature (T 10% ): 527℃ (in air), 520℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 48% Cutoff wavelength: 350nm Transmittance (500nm): 78% Average refractive index (n ave ):1.639(d line) Birefringence (Δn): 0.021 (d line) Permittivity (ε=n ave 2 ):2.69 Dielectric constant (Dk): 2.75 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.73 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0019 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0020 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 64 MPa Elongation at break: 19.4% Initial tensile modulus: 2.0 GPa That was the case.

[0094] (Example 10) The compound of Example 10, the polyether (BFPT-BisPCDE) shown below, was synthesized as follows. [ka] In Example 1, BisA was replaced with BisPCDE, and polymerization was carried out in NMP (5 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.

[0095] The yield was 96%, and the logarithmic viscosity was 0.51 dL / g (at 30°C, in a 0.5 g / dL DMPU solution).

[0096] The polymer was dissolved in DMPU, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 76 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3064(Ar-H),2937(CH),1592(C=C),1521(C=N),1501(C=C),1368(CN),1242(Ar-O) Elemental analysis (C 45 H 43 N3O2) n Calculated values: C, 82.16%; H, 6.59%; N, 6.39% Measured values: C, 82.25%; H, 6.65%; N, 6.32% Solubility: It was soluble in N,N'-dimethylpropylene urea (DMPU). Glass transition temperature (Tg): 272°C (DSC), 272°C (DMA) Coefficient of thermal expansion (CTE): 83 ppm / °C (in the range of 150 to 200°C) 5% weight loss temperature (T 5% ): 400℃ (in air), 443℃ (in nitrogen) 10% weight loss temperature (T 10% ): 443℃ (in air), 458℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 30% Cutoff wavelength: 350nm Average refractive index (n ave ):1.638(d line) Birefringence (Δn): 0.019 (d line) Permittivity (ε=n ave2 ):2.68 Dielectric constant (Dk): 2.67 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.66 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0020 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0017 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 54 MPa Elongation at break: 5.1% Initial tensile modulus: 1.6 GPa That was the case.

[0097] (Example 11) The compound of Example 11, the polyether (BFPT-DTPM) shown below, was synthesized as follows. [ka] In Example 1, BisA was replaced with DTPM, and polymerization was carried out in NMP (5.0 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.

[0098] The yield was 93%, the logarithmic viscosity was 0.69 dL / g (at 30°C, in a 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 63,000, the weight-average molecular weight (Mw) was 199,000, the molecular weight distribution (Mw / Mn) was 3.2, and the average degree of polymerization (n) was 95.

[0099] The polymer was dissolved in NMP, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 70 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3059(Ar-H),1592(C=C),1521(C=N),1499(C=C),1369(CN),1241(Ar-O) 1 H-NMR (CDCl3, ppm):8.68-8.64(m,6H),7.52-7.48(m,3H),7.29-7.20(m,14H),7.12(d,4H),6.98(d,4H) Elemental analysis (C 46 H 31 N3O2) n Calculated values: C, 83.99%; H, 4.75%; N, 6.39% Measured values: C, 84.07%; H, 4.85%; N, 6.32% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), cyclopentanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 263°C (DSC), 266°C (DMA) Coefficient of thermal expansion (CTE): 97 ppm / °C (in the range of 150 to 200°C) 5% weight loss temperature (T 5% ): 546℃ (in air), 543℃ (in nitrogen) 10% weight loss temperature (T 10% ): 558℃ (in air), 552℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 53% Cutoff wavelength: 352nm Transmittance (500nm): 68% Average refractive index (n ave ):1.682(d line) Birefringence (Δn): 0.017 (d line) Permittivity (ε=n ave 2 ):2.83 Dielectric constant (Dk): 2.82 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.82 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0018 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0017 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 70 MPa Elongation at break: 3.2% Initial tensile modulus: 1.6 GPa That was the case.

[0100] (Example 12) The compound of Example 12, the polyether (BFPT-BPFL) shown below, was synthesized as follows. [ka] In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6340 g, 1.84 mmol) and BPFL (0.6433 g, 1.84 mmol) were added. Potassium carbonate (0.3060 g, 2.20 mmol) was added as an alkali metal compound, N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove the water generated by the Dean-Stark trap. Then, the temperature was increased to 190°C and stirred for 1 hour to remove toluene. Polymerization was then carried out at 190°C for 2 hours. The mixture was cooled to room temperature to obtain a viscous polymerization solution. The polymer was precipitated by pouring it into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in NMP, poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0101] This compound yielded 1.134 g, had a yield of 94%, a logarithmic viscosity of 0.88 dL / g (at 30°C in a 0.5 g / dL NMP solution), and measured by the aforementioned GPC (THF) method, it had a number-average molecular weight (Mn) of 77,000, a weight-average molecular weight (Mw) of 206,000, a molecular weight distribution (Mw / Mn) of 2.7, and an average degree of polymerization (n) of 117.

[0102] This polymer was dissolved in TMU to prepare a 12 wt% solution. This solution was cast onto a glass plate and gradually heated to 160°C under reduced pressure, then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 64 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),1592(C=C),1519(C=N),1502(C=C),1368(CN),1241(Ar-O) 1 H-NMR (CDCl3, ppm):8.65-8.64(m,6H),7.75(d,2H),7.52-7.48(m,3H),7. 42(d,2H),7.35(t,2H),7.28(t,2H),7.17(d,4H),7.07(d,4H),6.93(d,4H) Elemental analysis (C 46 H 29 N3O2) n Calculated values: C, 84.25%; H, 4.46%; N, 6.41%; Measured values: C, 84.18%; H, 4.51%; N, 6.43%. Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, and cyclohexanone. Glass transition temperature (Tg): 309°C (DSC), 306°C (DMA) Coefficient of thermal expansion (CTE): 96 ppm / °C (in the range of 150 to 200°C) Temperature at which weight loss of 5% occurs: 516°C (in air), 568°C (in nitrogen). Temperature at which weight loss of 10% occurs: 525°C (in air), 578°C (in nitrogen). Carbonization yield: 58% (in nitrogen, 800°C) Cutoff wavelength: 353nm Transmittance at 500nm: 82% Average refractive index (n ave ):1.689(d line) Birefringence (Δn): 0.003 (d line) Permittivity (ε=n ave 2 ):2.85 Dielectric constant (Dk): 2.82 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.78 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0016 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0017 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 81 MPa Elongation at break: 4.4% Initial tensile modulus: 2.2G That was the case.

[0103] (Example 13) The compound of Example 13, the polyether (BFPT-DMBPFL) shown below, was synthesized as follows. [ka] In Example 1, BisA was replaced with DMBPFL, and polymerization was carried out in NMP (5.0 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.

[0104] The yield was 95%, the logarithmic viscosity was 0.91 dL / g (at 30°C, in a 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC(THF) was 87,000, the weight-average molecular weight (Mw) was 249,000, the molecular weight distribution (Mw / Mn) was 2.9, and the average degree of polymerization (n) was 127.

[0105] The polymer was dissolved in NMP, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 79 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1):3064(Ar-H),2921(CH),1588(C=C),1521(C=N),1509(C=C),1369(CN),1248(Ar-O) 1 H-NMR (CDCl3, ppm):8.68-8.64(m,6H),7.79(d,2H),7.54-7.47(m,5H),7.39( t,2H),7.32(t,2H),7.11-7.09(m,4H),6.99(d,4H),6.89(d,2H),2.11(s,6H) Elemental analysis (C 48 H 33 N3O2) n Calculated values: C, 84.31%; H, 4.87%; N, 6.15% Measured values: C, 84.40%; H, 4.98%; N, 6.12% Solubility: It was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and chloroform. Glass transition temperature (Tg): 298°C (DSC), 297°C (DMA) Coefficient of thermal expansion (CTE): 86 ppm / °C (range of 150 to 200°C) 5% weight loss temperature (T 5% ): 474℃ (in air), 450℃ (in nitrogen) 10% weight loss temperature (T 10% ): 522℃ (in air), 457℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 56% Cutoff wavelength: 354nm Transmittance (500nm): 75% Average refractive index (n ave ):1.678(d line) Birefringence (Δn): 0.012 (d line) Permittivity (ε=n ave 2 ):2.82 Dielectric constant (Dk): 2.78 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.81 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0019 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0017 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 73 MPa Elongation at break: 4.5% Initial tensile modulus: 2.3 GPa That was the case.

[0106] (Example 14) The compound of Example 14, the polyether (BFPT-TBISRX) shown below, was synthesized as follows. [ka] In Example 1, BisA was replaced with TBISRX, and polymerization was carried out in NMP (5.0 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.

[0107] The yield was 94%, the logarithmic viscosity was 0.68 dL / g (at 30°C, in a 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC (NMP) was 67,000, the weight-average molecular weight (Mw) was 253,000, the molecular weight distribution (Mw / Mn) was 3.8, and the average degree of polymerization (n) was 100.

[0108] The polymer was dissolved in NMP, cast onto a glass plate, and gradually heated to 160°C under reduced pressure. The plate was then dried under reduced pressure at 160°C for 3 hours. The glass plate was immersed in distilled water to remove the film, and the plate was dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 85 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3065(Ar-H),1595(C=C),1521(C=N),1486(C=C),1369(CN),1220(Ar-O) Solubility: Soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), and N,N'-dimethylimidazolidone (DMI). Glass transition temperature (Tg): 336°C (DSC), 335°C (DMA) Coefficient of thermal expansion (CTE): 61 ppm / °C (in the range of 150 to 200°C) 5% weight loss temperature (T 5% ): 579℃ (in air), 586℃ (in nitrogen) 10% weight loss temperature (T 10% ): 597℃ (in air), 596℃ (in nitrogen) Carbonization yield (in nitrogen, 800°C): 68% Cutoff wavelength: 351nm Transmittance (500nm): 72% Average refractive index (n ave ):1.689(d line) Birefringence (Δn): 0.015 (d line) Permittivity (ε=n ave 2 ):2.85 Dielectric constant (Dk): 2.81 (cavity resonator, TM mode, 10 GHz) Dielectric constant (Dk): 2.81 (cavity resonator, TE mode, 10 GHz) Dielectric loss tangent (Df): 0.0020 (cavity resonator, TM mode, 10 GHz) Dielectric loss tangent (Df): 0.0019 (cavity resonator, TE mode, 10 GHz) Tensile breaking strength: 78 MPa Elongation at break: 7.0% Initial tensile modulus: 2.4 GPa That was the case.

[0109] [Example of a sample exam] Below, we show a reference test using a reference example as another aspect of this embodiment.

[0110] (Test conditions) The following instruments and reagents were used for the synthesis of the samples and the analysis of the synthesized samples. The equipment and conditions used are as follows: (1) GPC: Tosoh Corporation high-speed GPC system HLC-8220GPC (Column: Tosoh TSKgel (α-M), Column temperature: 45℃, Eluent: N-methyl-2-pyrrolidone (NMP) (containing 0.01 mol / L lithium bromide), Calibration curve: Standard polystyrene, Column flow rate: 0.2 mL / min) (2) Infrared spectrum (FT-IR): FT / IR-4200 manufactured by JASCO Corporation (3) Nuclear magnetic resonance (NMR) spectroscopy: BRUKER AC400P (4) Thermogravimetric analysis (TGA): Hitachi High-Tech Science Corporation TG / DTA7300, heating rate 10°C / min (5) Differential scanning calorimetry (DSC): Hitachi High-Tech Science Corporation DSC7000, heating rate 20°C / min (6) Thermomechanical analysis (TMA): Hitachi High-Tech Science Co., Ltd. TMA7000, heating rate 10°C / min (7) Dynamic viscoelasticity measurement (DMA): DMA7100 manufactured by Hitachi High-Tech Science Corporation, heating rate 2°C / min (8) Tensile test: Shimadzu Corporation Autograph AGS-D type, tensile speed 10 mm / min (9) UV-Vis spectrophotometer: Shimadzu Corporation UV-1800 (10) Refractive index measurement: Metricon Model 2010 / M PRISM COUPLER (11) Dielectric constant measurement: AET dielectric constant / dielectric loss tangent measuring device (cavity resonator type), TE mode (10 GHz, 20 GHz) The reagents used were commercially available and purified by conventional methods as needed. The various reaction solvents were dried and purified by conventional methods as needed.

[0111] (Manufacturing of resin compositions) Among the compounds of formula (1) above, R = hydrogen (H) (BFPT), and Ar is, Compound of Bis A in formula (2) (BFPT-BisA, Reference Example 1), Compound of Bis AF in formula (3) (BFPT-BisAF, Reference Example 2) Compound of BisP-HTG in formula (4) (BFPT-PisP-HTG, Reference Example 3) Compound of BisP-IND in formula (5) (BFPT-BisP-IND, Reference Example 4) The compound was prepared. Furthermore, a compound was prepared in which R = hydrogen (H) (BFPT) and Ar = BPFL (9,9-bis(4-hydroxyphenyl)fluorene) from among the compounds of formula (1) above (BFPT-BPFL, Reference Example 5).

[0112] For the compounds of formula (6) and formula (7) used in the manufacturing process, the compound of formula (6) was a compound (BFPT) in which R = hydrogen (H). For the compound of formula (7), for each reference example, the compounds of formula (2) (Reference Example 1), formula (3) (Reference Example 2), formula (4) (Reference Example 3), and formula (5) (Reference Example 4) were used, with Ar being the compound of formula (2) (Reference Example 1), formula (3) (Reference Example 2), formula (4) (Reference Example 3), and formula (5) (Reference Example 4).

[0113] (Combination of each reference example) (BFPT compound) The 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine (BFPT) used in each reference example was synthesized as follows. In a three-necked flask (100 mL) equipped with a stirring bar and a nitrogen gas inlet tube, 7.460 g of 4-fluorobenzamidine hydrochloride, 42.73 mmol of benzylideneaniline, 3.625 g of benzylideneaniline, 3.781 g of sodium bicarbonate, and 35 mL of N,N-dimethylformamide (DMF) were added. The temperature was gradually increased to 85°C, and the mixture was reacted at 85°C for 96 hours. After cooling to room temperature, the mixture was added to distilled water and chloroform was added. The chloroform solution was washed three times with distilled water using a separatory funnel. The recovered chloroform solution was dried overnight over anhydrous sodium sulfate, and after removing the anhydrous sodium sulfate by suction filtration, the chloroform solution was concentrated using an evaporator and added to methanol (500 mL), at which point the crude product precipitated. This was collected by suction filtration, washed with methanol under reflux, and then dried under reduced pressure at room temperature to obtain a crude product (1.61 g, 23.3%) in the form of brown needle-shaped crystals. The crude product was recrystallized in a mixed solvent of chloroform and methanol and dried under reduced pressure at 80°C for 24 hours.

[0114] The synthesized compound had the following characteristics: shape: white needle-shaped crystals, yield: 1.46 g, yield: 21.1%, melting point: 259-262°C. Regarding this BFPT, the analysis results using the aforementioned equipment are: FT-IR (KBr, cm) -1 ):3051(Ar-H),1603 (C=C),1522 (C=N),1508(C=C),1370 (CN),1228 (Ar-F). 1 H-NMR (CDCl3, ppm):8.80-8.73 (m,6H),7.62 (t,1H),7.57 (t,2H),7.27-7.23 (m,4H). 13 C-NMR (CDCl3, ppm): 171.74,170.75,165.93,136.06,132.78,132.36,131.39,128.91,115.84 19 F-NMR (CDCl3, ppm): 108.41 Elemental analysis (C 21 H 13F2N3): Calculated values ​​were C, 73.03%; H, 3.79%; N, 12.17%. Measured values ​​were C, 72.94%; H, 4.00%; N, 12.15%.

[0115] (Reference example 1) The compound in Reference Example 1, polyether (BFPT-BisA), was synthesized as follows. In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and bisphenol A (0.4566 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N,N'-dimethylimidazolidone (DMI, 6.5 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water generated by the Dean-Stark trap. Then, the temperature was increased to 190°C and stirred for 2 hours to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was poured into methanol to precipitate, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in N-methyl-2-pyrrolidone (NMP), poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0116] As shown in the BFPT-BisA DMI table below, the yield was 0.618 g, the yield rate was 58%, the logarithmic viscosity was 0.54 dL / g (30°C, 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC was 30,000, the weight-average molecular weight (Mw) was 62,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[0117] This polymer was dissolved in NMP to prepare a 12 wt% solution. This solution was cast onto a glass plate, and the temperature was gradually increased to 200°C under reduced pressure. The solution was then dried under reduced pressure at 200°C for 3 hours to produce a colorless, transparent cast film (thickness 38 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3066(Ar-H),2968(CH),1592(C=C),1517(C=N),1504(C=C),1368(CN),1241(Ar-O). 1 H-NMR (CDCl3, ppm): 8.68(d,6H),7.53-7.50(m,3H),7.24(d,4H),7.09(d,4H),7.00(d,4H),1.69(s,6H). The cutoff wavelength was 353 nm, and the transmittance at 500 nm was 81%.

[0118] (Reference example 2) The compound in Reference Example 2, polyether (BFPT-BisAF), was synthesized as follows. In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and bisphenol AF (0.6725 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N,N'-dimethylimidazolidone (DMI, 6.5 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water generated by the Dean-Stark trap. Then, the temperature was increased to 190°C and stirred for 2 hours to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was poured into methanol to precipitate, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in tetramethylurea (TMU), poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0119] As shown in the BFPT-BisAF DMI table below, the yield was 1.021 g, the yield rate was 80%, the logarithmic viscosity was 0.98 dL / g (30°C, 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC was 106,000, the weight-average molecular weight (Mw) was 211,000, and the molecular weight distribution (Mw / Mn) was 2.0.

[0120] A polymer was dissolved in TMU to prepare a 9 wt% solution. This solution was cast onto a glass plate, and the temperature was gradually increased to 160°C under reduced pressure. The solution was then dried under reduced pressure at 160°C for 3 hours to produce a colorless, transparent cast film (thickness 37 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3064(Ar-H),1595(C=C),1518(C=N),1506(C=C),1368(CN),1248(Ar-O). 1 H-MNR (chloroform solvent, ppm): 8.74-8.69 (m,6H), 7.55-7.49 (m,3H), 7.42 (d,4H), 7.17 (d,4H), 7.07 (d,4H). Cutoff wavelength: 343nm, transmittance at 500nm: 83% Average refractive index (n): 1.621 (d line), birefringence (Δn): 0.022 (d line), dielectric constant calculated from refractive index (ε): 2.63 (ε=n 2 ) was.

[0121] (Reference example 3) The compound in Reference Example 3, polyether (BFPT-BisPHTG), was synthesized as follows. In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and BisPHTG (0.6209 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water generated by the Dean-Stark trap. Then, the temperature was increased to 190°C and stirred for 2 hours to remove toluene. Polymerization was then carried out at 190°C for 3 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was poured into methanol to precipitate, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in NMP and poured into methanol, allowing the white, flaky polymer to precipitate. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0122] As shown in the table below for BFPT-BisPHTG NMP, the yield was 1.163 g, the yield rate was 94%, the logarithmic viscosity was 0.48 dL / g (30°C, 0.5 g / dL NMP solution), the number-average molecular weight (Mn) measured by the aforementioned GPC was 74,000, the weight-average molecular weight (Mw) was 135,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[0123] This polymer was dissolved in tetramethylurea (TMU) to prepare a 15 wt% solution. This solution was cast onto a glass plate, and the temperature was gradually increased to 160°C under reduced pressure. The film was then dried under reduced pressure at 160°C for 3 hours to produce a colorless, transparent cast film (thickness 38 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),2948(CH),1593(C=C),1518(C=N),1504(C=C),1368(CN),1242(Ar-O). 1H-NMR (CDCl3, ppm):8.68-8.65(m,6H),7.52-7.48(m,3H),7.49(d,2H),7.23(d,2H),7.05(d,4H),7.00(d,2H),6.94(d,2H), 2.71(d,1H),2.47(d,1H),2.04-2.01(br,1H),1.96(d,1H),1.41(d,1H),1.20(t,1H),0.99(d,6H),0.89(d,1H),0.43(s,6H). Cutoff wavelength: 354nm, transmittance at 500nm: 81% Average refractive index (n): 1.637 (d line), birefringence (Δn): 0.006 (d line), dielectric constant calculated from refractive index (ε): 2.68 (ε=n 2 ) was.

[0124] (Reference example 4) The compound in Reference Example 4, polyether (BFPT-BisPIND), was synthesized as follows. In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6907 g, 2.00 mmol) and BisPIND (0.5368 g, 2.00 mmol) were added. Potassium carbonate (0.3334 g, 2.40 mmol) was added as an alkali metal compound, N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove water generated by the Dean-Stark trap. Then, the temperature was increased to 190°C and stirred for 2 hours to remove toluene. Polymerization was then carried out at 190°C for 3 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was precipitated by pouring it into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in NMP, poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0125] As shown in the table below for BFPT-BisP-IND NMP, the yield was 1.030 g, the yield yield was 90%, and the logarithmic viscosity was 0.96 dL / g (at 30°C, in a 0.5 g / dL NMP solution).

[0126] This polymer was dissolved in tetramethylurea (TMU) to prepare a 10 wt% solution. This solution was cast onto a glass plate, and the temperature was gradually increased to 160°C under reduced pressure. The film was then dried under reduced pressure at 160°C for 3 hours to produce a colorless, transparent cast film (thickness 43 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),2958(CH),1593(C=C),1518(C=N),1507(C=C),1368(CN),1239(Ar-O). 1 H-NMR (CDCl3, ppm):8.63-8.58(m,6H),7.46-7.42(m,3H),7.19-7.17(m,3H),7.07-7.04(m,2H), 7.00-6.96(m,5H),6.86(s,1H),2.42(d,1H),2.24(d,1H),1.67(s,3H),1.36(s,3H),1.11(s,3H). Cutoff wavelength: 352nm, transmittance at 500nm: 84% Average refractive index (n): 1.653 (d line), birefringence (Δn): 0.012 (d line), dielectric constant calculated from refractive index (ε): 2.73 (ε=n 2 ) was.

[0127] (Reference example 5) The compound in Reference Example 5, polyether (BFPT-BPFL), was synthesized as follows. In a two-necked flask (50 mL) equipped with a stirring bar and a nitrogen gas inlet tube, BFPT (0.6340 g, 1.84 mmol) and BPFL (0.6433 g, 1.84 mmol) were added. Potassium carbonate (0.3060 g, 2.20 mmol) was added as an alkali metal compound, N,N'-dimethylimidazolidone (DMI, 6.0 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and Liebig condenser were attached, and a nitrogen gas atmosphere was established. The temperature was gradually increased to 150°C with stirring, and toluene was refluxed at 150°C for 2 hours to remove the water generated by the Dean-Stark trap. The temperature was then increased to 190°C and stirred for 2 hours to remove toluene. Polymerization was then carried out at 190°C for 2 hours. After cooling to room temperature, a brown, viscous polymerization solution was obtained. The polymer was precipitated by pouring it into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The obtained polymer was dissolved in tetramethylurea (TMU), poured into methanol, and the white, flaky polymer precipitated. After recovering the polymer, it was dried under reduced pressure at room temperature.

[0128] This compound had a yield of 1.043 g, a yield of 87%, a logarithmic viscosity of 0.50 dL / g (at 30°C in a 0.5 g / dL NMP solution), a number-average molecular weight (Mn) of 46,000, a weight-average molecular weight (Mw) of 88,000, and a molecular weight distribution (Mw / Mn) of 1.9.

[0129] This polymer was dissolved in TMU to prepare a 12 wt% solution. This solution was cast onto a glass plate, and the temperature was gradually increased to 160°C under reduced pressure. The solution was then dried under reduced pressure at 160°C for 3 hours to produce a colorless, transparent cast film (thickness 64 μm). Regarding this example, the analysis results using the aforementioned equipment are as follows: FT-IR (film, cm) -1 ):3062(Ar-H),1593(C=C),1519(C=N),1502(C=C),1368(CN),1241(Ar-O). 1H-NMR (CDCl3, ppm):8.65-8.64(m,6H),7.75(d,2H),7.52-7.48(m,3H),7.4 2(d,2H),7.35(t,2H),7.28(t,2H),7.17(d,4H),7.07(d,4H),6.93(d,4H). Elemental analysis (C 49 H 29 O2N3) n Calculated values: C, 84.25%; H, 4.46%; N, 6.41%; Measured values: C, 84.18%; H, 4.51%; N, 6.43%. Solubility: Soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, and cyclohexanone. 5% weight loss temperature: 515°C (in air), 568°C (in nitrogen); 10% weight loss temperature: 521°C (in air), 578°C (in nitrogen); Carbonization yield: 58% (in nitrogen, 800°C); Glass transition temperature (Tg): 309°C (DSC), 331°C (TMA), 306°C (DMA). Tensile breaking strength: 68 MPa, Elongation at break: 4.2%, Initial tensile modulus: 5.0 GPa Cutoff wavelength: 353nm, transmittance at 500nm: 82% Average refractive index (n): 1.689 (d line), birefringence (Δn): 0.003 (d line), dielectric constant calculated from refractive index (ε): 2.85 (ε=n 2 ) The dielectric constant (Dk) was 2.89 (TE mode, 10 GHz) and 2.71 (TE mode, 20 GHz), and the dielectric loss tangent (Df) was 0.0024 (TE mode, 10 GHz) and 0.0025 (TE mode, 20 GHz).

[0130] (Reference Test Example 1: Investigation of Polar Solvents and Polymerization Temperatures) Reference Example 2 (BFPT-BisAF) was prepared under the same conditions as above, except that the polar solvent was changed to three types (NMP, TMU, DMI), the amount of solvent was changed to 5-7.5 mL, and the polymerization time was changed to 170-190°C. The polar solvent and polymerization temperature were investigated. The results are shown in Table 1. The yield is the value after the reprecipitation. Logarithmic viscosity (η) inh The values ​​were measured at 30°C using a 0.5 g / dL NMP solution.

[0131] [Table 1]

[0132] As shown in Table 1, using DMI as the polar solvent, with a volume of 5 mL of the polar solvent (i.e., 25% by volume relative to 20 mL of toluene), and a polymerization temperature of 190°C, high yield and high logarithmic viscosity were obtained. Furthermore, using 6.5 mL of the polar solvent yielded extremely high yield and extremely high logarithmic viscosity. On the other hand, when the polymerization temperature was 170-180°C and NMP or TMU were used as the polar solvent, the yield and logarithmic viscosity decreased slightly, and discoloration was observed, but production was still possible.

[0133] (Reference Test Example 2: Synthetic study of compounds from Reference Examples 1-4) The compounds in Reference Examples 1-4 were synthesized under the conditions described above. For each Reference Example, the synthesis was carried out using the same procedure, except that DMI was replaced with NMP. The results are shown in Tables 2 and 3.

[0134] [Table 2] [Table 3]

[0135] In addition to Reference Example 2 synthesized in Reference Test Example 1, Reference Examples 1 through 4 could each be synthesized with a consistently high yield. For all of Reference Examples 1, 3, and 4, using NMP resulted in higher yields, logarithmic viscosity, and number-average molecular weight (Mn), as well as less discoloration.

[0136] Furthermore, Figure 1 shows the FT-IR spectra of Reference Examples 1-4, which were synthesized using DMI in a polar solvent, as measured using the aforementioned instrument.

[0137] Table 4 shows the results of elemental analysis performed on each reference example. In the table, "Calcd." represents the calculated value, and "Found." represents the measured value.

[0138] [Table 4]

[0139] (Reference Test Example 3: Solubility of Compounds from Reference Examples 1-4) Tables 5 and 6 show the results of solubility tests conducted on the compounds in Reference Examples 1-4 at room temperature or after heating. Solubility was measured at 10 mg / 5.0 mL. ++: It was soluble at room temperature. +: It dissolved when heated. +-: Only a portion dissolved. -: It was insoluble.

[0140] [Table 5] [Table 6]

[0141] Reference Example 1 was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), and N,N'-dimethylimidazolidone (DMI). Reference Example 2 was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), N,N-dimethylacetamide (DMAc), chloroform, tetrahydrofuran (THF), cyclopentanone, and cyclohexanone. Reference Example 3 was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, and cyclohexanone. Reference Example 4 was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, and cyclohexanone. Although not shown in the table, Reference Example 5 was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, and cyclohexanone. In particular, the reference examples demonstrated that although the compounds are stable, they are soluble in certain organic solvents and are excellent for reprecipitation purification and molding processes.

[0142] (Reference Test Example 4: Thermal Properties of Compounds from Reference Examples 1-4) Tables 7 and 8 show the results of examining the thermal properties of the compounds in Reference Examples 1 to 4, using the aforementioned thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and dynamic viscoelasticity measurement (DMA). Table 7 shows the glass transition temperature (Tg) and thermal expansion coefficient (CTE). The glass transition temperature was measured by DSC in nitrogen at a heating rate of 20°C / min, by TMA in nitrogen at a heating rate of 10°C / min, and by DMA in nitrogen at a heating rate of 2°C / min. The CTE was measured by TMA at 150-200°C. Table 8 T 5% , T 10% These values ​​represent the 5% and 10% depletion temperatures, respectively, and were measured by TGA in nitrogen or air at a heating rate of 10°C / min. Char yield is the carbonization yield, expressed as weight % at 800°C in nitrogen.

[0143] [Table 7] [Table 8]

[0144] As shown in Table 7, each reference example exhibited high heat resistance, with a glass transition temperature of around 240°C or higher. The results in Table 8 show that 5% and 10% thermal decomposition occurred at temperatures above 400°C in air and above 500°C in nitrogen, indicating high thermal stability.

[0145] (Reference Test Example 5: Dielectric Properties of Compounds from Reference Examples 1-4) Table 9 shows the results of examining the dielectric properties of the compounds in Reference Examples 1 to 4 under the dielectric constant measurement conditions described above. In Table 9, n represents the refractive index measured using a prism coupler, measured at the F line (486 nm), d line (588 nm), and C line (656 nm). TE mode represents the refractive index in the plane of the film, and TM mode represents the refractive index out of the plane of the film. V d n is the Abbe number. ave is n ave =[(2n TE 2 +n TM 2 ) / 3] 1 / 2 The average refractive index is obtained by n TE and n TM The refractive indices for each mode are measured at the d-line (588 nm). The dielectric constant (ε) is given by ε = n ave 2 These are the values ​​obtained. The dielectric constant (Dk) and dielectric loss tangent (Df) were measured using a cavity resonator.

[0146] [Table 9]

[0147] Table 9 shows that in all of the reference examples 1 to 4, the Dk (dielectric constant) is 2.6 or less and the Df (dielectric loss tangent) is 0.003 or less, indicating that these values ​​are sufficiently low. Although not shown in the table, in Reference Example 5, the dielectric loss tangent (Df) was 0.0024 (TE mode, 10 GHz) and 0.0025 (TE mode, 20 GHz), and values ​​below 0.003 were observed. However, the dielectric constant (Dk) was 2.89 (TE mode, 10 GHz) and 2.71 (TE mode, 20 GHz), which were higher than those in Reference Examples 1-4.

[0148] (Reference Test Example 6: Mechanical Properties of Compounds from Reference Examples 1-4) Table 10 shows the results of examining the mechanical properties of the compounds in Reference Examples 1 to 4 under the tensile test conditions described above. The tensile test was performed at a tensile speed of 10 mm / min, using the 5 mm x 30 mm cast film as described in each of the synthesis processes mentioned above. Ts represents the tensile breaking strength, Eb represents the elongation at breaking, and Tm represents the initial tensile modulus.

[0149] [Table 10]

[0150] In Table 10, all of Reference Examples 1 to 4 demonstrated sufficient tensile mechanical properties. [Industrial applicability]

[0151] According to the present invention, a resin composition and a method for producing the same can be obtained that are suitable for use as a low dielectric material because they have a low dielectric constant, a low dielectric loss tangent, high transparency, high solubility, and high heat resistance.

Claims

1. The compound comprises a triazine-containing polyether compound having repeating units represented by the following general formula (1), The aforementioned triazine-containing polyether compound is The number-average molecular weight (Mn) is 3 × 10⁻⁶ ３ ~40 x 10 ４ And, Weight-average molecular weight (Mw) is 6 × 10 ３ ~40 x 10 ４ And, Measurements of the cavity resonator in TE mode (10 GHz) showed that the dielectric constant Dk was 2.8 or less, or the dielectric loss tangent Df was 0.003 or less. The glass transition temperature determined by differential scanning calorimetry (DSC) is 200°C or higher. The triazine-containing polyether compound is one in which Ar in the following general formula (1) is represented by any of the following general formulas (5), (8), (10), (11), (14), or (15). Resin compositions for low dielectric materials. 【Chemistry 1】 [In formula (1), n ​​is an integer between 2 and 200, and Ar refers to a phenylene group, a naphthylene group, or a biphenylene group, or an arylene group to which an alkyl group, alkylene group, alkylidene group, cycloalkyl group, cycloalkylene group, cycloalkylidene group, aryl group, arylene group, fluorinated alkyl group, fluorinated alkylene group, fluorinated aryl group, or fluorinated arylene group is bonded. R represents hydrogen, a linear, branched, or cyclic aliphatic group, an aromatic group with or without substituents, a fluorinated aliphatic group, or a fluorinated aromatic group.] 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】

2. The resin composition for low dielectric materials according to claim 1, comprising the triazine-containing polyether compound and an epoxy resin, a bismaleimide resin, or a cyanate resin.

3. A resin composition for low dielectric materials according to claim 1 or 2, further comprising an inorganic filler, a modifier, or a flame retardant.

4. A resin composition for low dielectric materials according to any one of claims 1 to 3, used in equipment that transmits and receives high-frequency electromagnetic waves having a frequency of 0.1 to 500 GHz.

5. A resin composition for low dielectric materials according to any one of claims 1 to 4, for use in printed circuit boards, flexible printed circuit boards, encapsulants for electronic components, resist inks, conductive pastes, insulating materials, or insulating boards.

6. A film for a laminated substrate having at least one surface an insulating material comprising the resin composition for low dielectric materials described in any one of claims 1 to 5.

7. A laminated substrate comprising two or more laminated substrate films as described in claim 6.

8. A method for producing a resin composition for low dielectric materials according to any one of claims 1 to 5, A method for producing a resin composition for low dielectric materials, comprising mixing a compound represented by the following general formula (16) and a compound represented by the following general formula (17), polymerizing them to obtain a triazine-containing polyether compound represented by the following general formula (18), and obtaining the triazine-containing polyether compound. 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 [In formulas (16), (17), and (18), n is an integer of 2 or more, Ar represents a divalent aromatic group with or without substituents, R represents hydrogen, a linear, branched, or cyclic aliphatic group, an aromatic group with or without substituents, a fluorinated aliphatic group, or a fluorinated aromatic group.]

9. A method for producing a resin composition for a low dielectric material used as an insulating material between layers of a laminated substrate, A method for producing a resin composition for a low dielectric material according to claim 8, comprising mixing the triazine-containing polyether compound, an epoxy resin, a bismaleimide resin or a cyanate resin, a curing accelerator, and an organic solvent.

10. A method for producing a resin composition for a low dielectric material according to claim 9, further comprising mixing an inorganic filler, a modifier, or a flame retardant.

11. A method for manufacturing a laminated substrate film, comprising applying an insulating material containing a resin composition for low dielectric materials, manufactured by the method for manufacturing a resin for low dielectric materials described in claim 9 or 10, to at least one surface of a resin film.

12. A method for manufacturing a laminated substrate, comprising stacking two or more films for a laminated substrate, each produced by the method for manufacturing a laminated substrate according to claim 11.

13. A resin composition for low dielectric materials according to any one of claims 1 to 4, for use in resin compositions for copper-clad laminates, interlayer insulating materials for build-up printed circuit boards, build-up films, resin compositions for encapsulants of electronic components, resin compositions for resist inks, binders for friction materials, conductive pastes, resin casting materials, adhesives, insulating paints, or coating materials.

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