Fluorinated polyamide compounds, fluorinated polyimide compounds, low dielectric materials, and high-frequency electronic components

Abstract

The present disclosure provides fluorinated polyamide compounds and fluorinated polyimide compounds having specific repeating units.

Description

[Technical Field]

[0001] This disclosure relates to fluorinated polyamide compounds, fluorinated polyimide compounds, low dielectric materials, and high-frequency electronic components. [Background technology]

[0002] Patent Document 1 describes a fluorinated nitrogen-containing heterocyclic compound having a repeating unit represented by formula (3). [ka] (In formula (3), n is an integer between 4 and 8, Rf represents a single bond, -SO2-, -O-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group, and ring C represents an imide ring or benzimidazole ring which may have substituents.) [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-178956 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] This disclosure aims to provide a soluble fluorinated polyamide compound that can be obtained having a low dielectric constant and a low dielectric loss tangent. [Means for solving the problem]

[0005] According to a first aspect of this disclosure, a fluorinated polyamide compound having repeating units represented by formula (1) is provided. Formula (1): [ka] (In formula (1), n ​​is an integer from 1 to 8, ring A and ring B are independently substituted or unsubstituted hydrocarbon rings, R is independently H, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a linking group, R 1 (Each represents independently an OH group, a optionally substituted linear or branched alkoxy group, an optionally substituted aromatic oxy group, or a halogen atom.) [Effects of the Invention]

[0006] According to this disclosure, it is possible to provide a soluble fluorinated polyamide compound that can be obtained having a low dielectric constant and a low dielectric loss tangent. Furthermore, according to this disclosure, it is possible to provide a fluorinated polyamide compound that has a low dielectric constant and a low dielectric loss tangent. [Modes for carrying out the invention]

[0007] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.

[0008] <Fluorinated polyamide compounds> The fluorinated polyamide compounds of this disclosure have repeating units represented by formula (1). Formula (1): [ka] (In formula (1), n ​​is an integer from 1 to 8, ring A and ring B are independently substituted or unsubstituted hydrocarbon rings, R is independently H, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a linking group, R 1(Each represents independently an OH group, a optionally substituted linear or branched alkoxy group, an optionally substituted aromatic oxy group, or a halogen atom.)

[0009] The fluorinated polyamide compounds of this disclosure contain repeating units represented by formula (1), wherein ring B is a linear perfluoroalkylene group (-(CF2) n Because the bond is via a perfluoroisopropylidene group (-C(CF3)2-), the fluorinated polyimide compounds derived from the fluorinated polyamide compound of formula (1) have even lower dielectric constants and dielectric loss tangents compared to conventional fluorinated polyimide compounds derived from conventional fluorinated polyamide compounds in which ring B is bonded via a perfluoroisopropylidene group (-C(CF3)2-). Furthermore, the fluorinated polyamide compounds of this disclosure are soluble in organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

[0010] n represents an integer from 1 to 8. Preferably, n is an integer from 4 to 8, and more preferably from 4 to 6, because it allows for even lower dielectric constant and dielectric loss tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound.

[0011] Ring A is a hydrocarbon ring with or without substituents. Preferred rings for Ring A are a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring, with a benzene ring being more preferred.

[0012] Ring B is a hydrocarbon ring with or without substituents. Preferred rings for ring B are a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring, with a benzene ring being more preferred.

[0013] R is independently H, a linear, branched, or cyclic aliphatic group, an aromatic group with or without substituents, a linear, branched, or cyclic fluorinated aliphatic group, or an unsubstituted fluorinated aromatic group. H is preferred as R.

[0014] L is a linking group. L is preferably a single bond, -O-, -SO2-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group, with a divalent fluorinated organic group being more preferred.

[0015] The above-mentioned non-fluorinated organic group is a divalent organic group that does not contain a fluorine atom. A linear or branched non-fluorinated alkylene group or a non-fluorinated arylene group is preferred as the above-mentioned non-fluorinated organic group.

[0016] The above-mentioned fluorinated organic group is a divalent organic group having one or more fluorine atoms. A linear or branched fluorinated alkylene group or a fluorinated arylene group is preferred as the above-mentioned fluorinated organic group.

[0017] As for L, linear or branched fluorinated alkylene groups are preferred, and perfluoroalkylene groups are more preferred, because they can further lower the dielectric constant and dielectric loss tangent of fluorinated polyimide compounds derived from fluorinated polyamide compounds. The number of carbon atoms in the perfluoroalkylene group is preferably 1 to 8.

[0018] As the above-mentioned fluorinated alkylene group, the perfluoroalkylene group represented by the following formula is more preferred because it can further lower the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound. Formula:-(CF2) n1 - (In the formula, n1 represents an integer between 1 and 8.)

[0019] As n1, since it can further lower the dielectric constant and dielectric tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound, it is preferably an integer of 4 to 8, more preferably 4 to 6, and still more preferably 4 or 6.

[0020] R 1 is, independently, OH, a linear or branched alkoxy group which may have a substituent, an aromatic oxy group which may have a substituent, or a halogen atom.

[0021] R 1 The number of carbon atoms of the alkoxy group as R is preferably 1 to 12, and more preferably 1 to 6.

[0022] R 1 As the substituents that the alkoxy group and the aromatic oxy group as R may have, an alkyl group, a fluorinated alkyl group, an alkoxy group, a fluorinated alkoxy group, a halo group (halogen atom), a nitro group, a cyano group or an ester group are preferable, and an alkoxy group is more preferable.

[0023] R 1 Examples of the aromatic oxy group as R include a phenoxy group without a substituent, a triazinyl oxy group which may have a substituent, etc.

[0024] R 1 is, independently, OH, a phenoxy group without a substituent, a methoxy group, an ethoxy group, a chlorine atom, or

Chemical formula

[0025] The repeating unit represented by formula (1) is preferably the repeating unit represented by formula (1-1). Formula (1-1):

Chemical formula

[0026] Examples of fluorinated polyamide compounds include those represented by the following formula. [ka] (wherein n, L and R 1 This is as stated above. R 2 Each independently represents either H or a monovalent organic group. The average degree of polymerization of the repeating units shown in formula (1) may have the repeating units shown in parentheses.

[0027] R 2 These are independently H or a monovalent organic group. A monovalent organic group is a monovalent group containing a carbon atom, or a group formed by removing one hydrogen atom from an organic compound. Examples of the above monovalent organic groups include optionally substituted aliphatic hydrocarbon groups, optionally substituted aromatic groups, optionally substituted aliphatic hydrocarbon acyl groups, optionally substituted aromatic acyl groups, and the like.

[0028] Specific examples of the above monovalent organic groups include lower alkyl groups having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms, such as -CH3, -C2H5, and -C3H7; fluorine-containing lower alkyl groups having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms, such as -CF3, -C2F5, -CH2F, -CH2CF3, and -CH2C2F5; phenyl groups (without substituents); benzyl groups (without substituents); phenyl or benzyl groups in which 1 to 5 hydrogen atoms are substituted with fluorine atoms, such as -C6F5 and -CH2C6F5; and -C6H 5-k (CF3) k -CH2C6H 5-k (CF3) kExamples include phenyl or benzyl groups in which 1 to 5 hydrogen atoms are substituted with -CF3 (where k is an integer from 1 to 5); aliphatic acyl groups such as acetyl and pivaloyl groups; aromatic acyl groups such as benzoyl and methylbenzoyl groups; fluorinated acetyl groups such as fluoroacetyl and trifluoroacetyl groups; and fluorobenzoyl and trifluoromethylbenzoyl groups.

[0029] R 2 The preferred elements are, independently, H or optionally substituted aromatic groups, more preferably H or optionally substituted phenyl groups, and even more preferably H, an unsubstituted phenyl group, or a phenyl group substituted with a fluorine atom-containing alkyl group having 1 to 10 carbon atoms.

[0030] In the fluorinated polyamide compounds of this disclosure, the average degree of polymerization of the repeating units represented by formula (1) is preferably 500 or less, more preferably 300 or less, even more preferably 200 or less, and may be 2 or more, or 3 or more. The average degree of polymerization is calculated from the number-average molecular weight of the fluorinated polyamide compounds of this disclosure.

[0031] The number-average molecular weight (Mn) of the fluorinated polyamide compounds of this disclosure is preferably 2,000 or more, more preferably 10,000 or more, more preferably 1,000,000 or less, and more preferably 500,000 or less, based on standard polystyrene as measured by gel permeation chromatography.

[0032] The molecular weight distribution (Mw / Mn) of the fluorinated polyamide compounds of this disclosure is preferably 1.5 or higher, more preferably 2 or higher, more preferably 5 or lower, and more preferably 4 or lower, based on standard polystyrene equivalent as determined by gel permeation chromatography.

[0033] Logarithmic viscosity η of the fluorinated polyamide compound disclosed herein inh The logarithmic viscosity η is preferably 0.3 dL / g or more, and more preferably 0.5 dL / g or more. inhThe viscosity can be calculated by dissolving a fluorinated polyamide compound in a solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a solution with a concentration of 0.5 g / dL, measuring the viscosity of the resulting solution at 30°C (solution viscosity), and using the following formula. Logarithmic viscosity η inh = ln(solution viscosity / solvent viscosity) / solution concentration

[0034] The fluorinated polyamide compounds of this disclosure can be suitably used as precursors to fluorinated polyimide compounds having repeating units represented by formula (2), as described later.

[0035] <Fluorinated polyimide compounds> The fluorinated polyimide compounds of this disclosure have repeating units represented by formula (2). Formula (2): [ka] (In equation (2), n, ring A, ring B, R, and L are the same as in equation (1).)

[0036] The fluorinated polyimide compounds of this disclosure contain repeating units represented by formula (2), wherein ring B is a linear perfluoroalkylene group (-(CF2) n Because the ring B is bonded via a perfluoroisopropylidene group (-C(CF3)2-), the dielectric constant and dielectric loss tangent are even lower compared to conventional fluorinated polyimide compounds in which ring B is bonded via a perfluoroisopropylidene group (-C(CF3)2-).

[0037] In formula (2), n, ring A, ring B, R, and L are the same as in formula (1), and by using the same preferred configuration as in formula (1), the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound can be further reduced.

[0038] The repeating unit shown in formula (2) is preferably the repeating unit shown in formula (2-1). Formula (2-1): [ka] (In equation (2-1), n ​​and L are as described above.)

[0039] Examples of fluorinated polyimide compounds include those represented by the following formula. [ka] (In the formula, n, L, R 1 and R 2 As stated above, the average degree of polymerization of the repeating units shown in equation (2) may include the repeating units shown in parentheses.

[0040] The dielectric loss tangent (Df) of the fluorinated polyimide compound of this disclosure at 10 GHz is preferably 0.005 or less, and more preferably 0.0045 or less.

[0041] The glass transition temperature of the fluorinated polyimide compounds of this disclosure is preferably 50 to 400°C, more preferably 100 to 350°C, and even more preferably 150 to 260°C. The glass transition temperature is a value measured by differential scanning calorimetry (DSC), dynamic viscoelasticity measurement (DMA), or thermomechanical analysis (TMA).

[0042] In the fluorinated polyimide compounds of this disclosure, the average degree of polymerization of the repeating units represented by formula (2) is preferably 300 or less, more preferably 200 or less, and may be 2 or more, or 3 or more. The average degree of polymerization is calculated from the number-average molecular weight of the fluorinated polyimide compounds of this disclosure.

[0043] Since the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound can be further reduced, the fluorinated polyimide compound may be a polymer with a relatively high average degree of polymerization, for example, a polymer with an average degree of polymerization of more than 100.

[0044] The number-average molecular weight (Mn) of the fluorinated polyimide compounds of this disclosure is preferably 2,000 or more, more preferably 10,000 or more, more preferably 1,000,000 or less, and more preferably 500,000 or less, based on standard polystyrene as determined by gel permeation chromatography.

[0045] The molecular weight distribution (Mw / Mn) of the fluorinated polyimide compound of this disclosure is preferably 1.5 or higher, more preferably 2 or higher, preferably 5 or lower, and more preferably 4 or lower, based on standard polystyrene equivalent as determined by gel permeation chromatography.

[0046] Logarithmic viscosity η of the fluorinated polyimide compound disclosed herein inh The logarithmic viscosity η is preferably 0.3 dL / g or more, and more preferably 0.5 dL / g or more. inh The viscosity can be calculated by dissolving a fluorinated polyimide compound in a solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a solution with a concentration of 0.5 g / dL, measuring the viscosity of the resulting solution at 30°C (solution viscosity), and using the following formula. Logarithmic viscosity η inh = ln(solution viscosity / solvent viscosity) / solution concentration

[0047] <Method for producing fluorinated polyamide compounds> The fluorinated polyamide compounds of this disclosure can be suitably produced by polymerizing compound (3) represented by formula (3) and compound (4) represented by formula (4).

[0048] Formula (3): [ka] (In formula (3), rings A, L and R 2 (As stated above.)

[0049] Formula (4): [ka] (In formula (4), n, ring B, R and R 1As stated above, in equation (4), two adjacent -COR 1 These two -COR compounds bond to each other via acid anhydride bonds (-CO-O-CO-). 1 (It may form a ring with the two carbon atoms to which it is bonded.)

[0050] Compound (3) is preferably compound (3-1) represented by formula (3-1). Formula (3-1): [ka] (In equation (3-1), L and R 2 (As stated above.)

[0051] As compound (4), compound (4-1) represented by formula (4-1) is preferred. Formula (4-1): [ka] (In equation (4-1), n ​​and R 1 As stated above, in equation (4-1), two adjacent -COR 1 These two -COR compounds bond to each other via acid anhydride bonds (-CO-O-CO-). 1 (It may form a ring with the two carbon atoms to which it is bonded.)

[0052] Polymerization of compound (3) and compound (4) can be carried out in a solvent. The solvent should not substantially react with compound (3) and compound (4), and should have the property of dissolving compound (3) and compound (4) well, and should also be a good solvent for the fluorinated polyimide compound obtained by polymerizing compound (3) and compound (4). Such solvents are not particularly limited, but examples include dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU), cyclohexanone, cyclopentanone, sulfolane, tetrahydrofuran (THF), and acetone. Among these, N-methyl-2-pyrrolidone (NMP) and 1,3-dimethylimidazolidone (DMI) are preferred. The amount of these solvents used is typically 100 to 1000 mL, preferably 50 to 400 mL, per 0.1 mole of compound (3) or compound (4).

[0053] Polymerization can also be carried out in the presence of additives. For example, inorganic salts such as lithium chloride or calcium chloride may be added to obtain compounds with high molecular weight. Among these additives, lithium chloride is preferred. The amount of additive added is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the amount of solvent.

[0054] Polymerization can be carried out, for example, by dissolving either compound (3) or compound (4) in a solvent, adding the other compound to the resulting solution, and then reacting under an inert atmosphere such as nitrogen while stirring. The polymerization temperature is preferably -50 to 150°C, more preferably 0 to 100°C, and even more preferably 20 to 80°C. The polymerization time is preferably 0.1 to 50 hours, and more preferably 1 to 24 hours.

[0055] The average degree of polymerization of the repeating units shown in equation (1) can be controlled by adjusting the molar ratio of compound (3) and compound (4), polymerization temperature, polymerization time, polymerization solution concentration, etc.

[0056] The above manufacturing method typically yields a polymerization solution of a fluorinated polyamide compound. The obtained polymerization solution of the fluorinated polyamide compound may be used as is for various applications. Alternatively, the obtained solution of the fluorinated polyamide compound may be separated from the fluorinated polyamide compound by dissolving it in a poor solvent such as methanol or water, and then purified by reprecipitation to remove by-products and inorganic salts, thereby obtaining a highly pure fluorinated polyamide compound.

[0057] <Method for producing fluorinated polyimide compounds> The fluorinated polyimide compounds of this disclosure can be suitably produced by obtaining a fluorinated polyamide compound by the above production method, and then dehydrating and cyclizing the fluorinated polyamide compound. Furthermore, when the polymerization of compound (3) and compound (4) is carried out under heated conditions during the production of the fluorinated polyamide compound, some or all of the compound may undergo dehydration and cyclization to form a compound having repeating units represented by formula (2), and as a result, the fluorinated polyimide compound of this disclosure may be obtained as some or all of the product. In other words, this disclosure also includes fluorinated polyamide compounds and mixtures of fluorinated polyimide compounds.

[0058] Dehydration and cyclization of fluorinated polyamide compounds can be carried out by heating the fluorinated polyamide compound. The heating temperature for dehydration and cyclization is preferably 110 to 450°C, and more preferably 150 to 350°C. The heating time is preferably 0.1 to 10 hours, and more preferably 0.5 to 8 hours. Dehydration and cyclization can be carried out in air, a nitrogen or argon atmosphere, or under reduced pressure.

[0059] The fluorinated polyimide compounds of this disclosure have a low dielectric constant and a low dielectric loss tangent, making them suitable for use as low-dielectric materials, as are fluorinated polyamide compounds and fluorinated polyimide compounds.

[0060] The fluorinated polyimide compounds of this disclosure have a low dielectric constant and a low dielectric loss tangent, making them suitable for use as semiconductor package substrates, flexible printed circuit boards, and rigid printed circuit boards.

[0061] The fluorinated polyimide compounds of this disclosure have a low dielectric constant and a low dielectric loss tangent, making them suitable for use as materials for semiconductor package wiring boards, flexible printed wiring boards, rigid printed wiring boards, TAB tapes, COF tapes, or metal wiring, as well as cover substrates for metal wiring, chip components such as IC chips, interlayer insulating films for liquid crystal displays, organic electroluminescent displays, electronic paper, and solar cells, base substrates, adhesive sheets, prepregs, primers, and other electronic components and electronic equipment.

[0062] The fluorinated polyimide compounds of this disclosure have particularly low dielectric constants and low dielectric loss tangents at high frequencies, making them suitable for use as materials for electronic components and electronic equipment utilizing high frequencies, especially microwaves in the 3-30 GHz range. For example, they are suitable for use as materials for high-frequency electronic components, insulating boards for high-frequency circuits, insulating materials for connecting components, printed circuit boards, bases and antenna covers for high-frequency vacuum tubes, coaxial cables, and insulated wires such as LAN cables. They are also suitable for use as materials for equipment such as satellite communication equipment and mobile phone base stations that utilize microwaves in the 3-30 GHz range.

[0063] Printed circuit boards are not particularly limited, but examples include printed wiring boards for electronic circuits in mobile phones, smartphones, various computers, and communication devices.

[0064] The coaxial cable is not particularly limited, but examples include one having a structure in which an inner conductor, an insulating coating layer, an outer conductor layer, and a protective coating layer are laminated in order from the core to the outer periphery.

[0065] The fluorinated polyimide compounds of this disclosure have low dielectric constant and low dielectric loss tangent, as well as excellent heat resistance, solvent solubility, electrical insulation, colorless transparency, and flexibility, and are easy to form into thin films. Therefore, fluorinated polyamide compounds and fluorinated polyimide compounds can be suitably used in interlayer insulating films, films, adhesive sheets, prepregs, primers, polymer electrolyte films, resist materials, etc. They are particularly suitable for use in films.

[0066] The above-mentioned film can be produced by molding the fluorinated polyamide compound or fluorinated polyimide compound of the present invention using known film molding methods such as extrusion molding, calendering, or solution casting. Alternatively, by casting a solution containing the fluorinated polyamide compound of the present invention and heating it, the formation of a fluorinated polyimide compound through dehydration cyclization of the fluorinated polyamide compound and the formation of a film can be carried out simultaneously. Furthermore, the film may be subjected to sandblasting, corona treatment, plasma treatment, etching, or other treatments.

[0067] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0068] <1> According to the first aspect of this disclosure, A fluorinated polyamide compound having repeating units represented by formula (1) is provided. Formula (1): [ka] (In formula (1), n ​​is an integer from 1 to 8, ring A and ring B are independently substituted or unsubstituted hydrocarbon rings, R is independently H, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a linking group, R 1 (Each represents independently an OH group, a optionally substituted linear or branched alkoxy group, an optionally substituted aromatic oxy group, a siloxy group, or a halogen atom.) <2> According to the second aspect of this disclosure, A fluorinated polyamide compound is provided in a first aspect, wherein ring A is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring. <3> According to the third aspect of this disclosure, A fluorinated polyamide compound is provided in a first or second view, wherein ring B is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring. <4> According to the fourth aspect of this disclosure, A fluorinated polyamide compound is provided in any of the first to third views, wherein L is a single bond, -O-, -SO2-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group. <5> According to the fifth aspect of this disclosure, A fluorinated polyamide compound is provided in which the repeating unit shown in formula (1) is the repeating unit shown in formula (1-1) according to any of the first to fourth viewpoints. Formula (1-1): [ka] (In equation (1-1), n, L and R 1 (As stated above.) <6> According to the sixth aspect of this disclosure, A fluorinated polyimide compound having repeating units represented by formula (2) is provided. Formula (2): [ka] (In formula (2), n is an integer from 1 to 8, ring A and ring B are independently substituted or unsubstituted hydrocarbon rings, R is independently H, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, and L is a linking group.) <7> According to the seventh aspect of this disclosure, A fluorinated polyimide compound is provided in a sixth aspect, wherein ring A is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring. <8> According to the eighth aspect of this disclosure, A fluorinated polyimide compound is provided in a sixth or seventh aspect, wherein ring B is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring. <9> According to the ninth aspect of this disclosure, Fluorinated polyimide compounds are provided in any of the sixth to eighth views, wherein L is a single bond, -O-, -SO2-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group. <10> According to the tenth aspect of this disclosure, A fluorinated polyimide compound is provided in which the repeating unit shown in formula (2) is the repeating unit shown in formula (2-1), according to any of the sixth to ninth viewpoints. Formula (2-1): [ka] (In equation (2-1), n ​​and L are as described above.) <11> According to the eleventh aspect of this disclosure, A fluorinated polyimide compound is provided that has a dielectric loss tangent (Df) of 0.005 or less at 10 GHz, according to any of the sixth to tenth aspects. <12> According to the 12th aspect of this disclosure, A low dielectric material is provided that contains a fluorinated polyamide compound according to any of the first to fifth aspects, or a fluorinated polyimide compound according to any of the sixth to eleventh aspects. <13> According to the 13th aspect of this disclosure, A high-frequency electronic component is provided that contains a fluorinated polyamide compound according to any of the first to fifth aspects, or a fluorinated polyimide compound according to any of the sixth to eleventh aspects. [Examples]

[0069] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.

[0070] Each value in the examples was measured by the following method.

[0071] (1) GPC: Tosoh Corporation high-speed GPC system HLC-8220GPC (Column: Tosoh TSKgel (α-M), Column temperature: 45℃, Detector: UV-8020, Wavelength: 254nm, 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) UV-Vis spectrophotometer: Shimadzu Corporation UV-1800 (9)Refractive index measurement: Metricon Model 2010 / M PRISM COUPLER (10) Dielectric constant measurement: AET dielectric constant / dielectric loss tangent measuring device (Anritsu network analyzer MS46122B, cavity resonator TE mode 10GHz and 20GHz, cavity resonator TM mode 10GHz)

[0072] <Synthesis Example 1> Synthesis of 4,4'-(1,6-perfluorohexylene)dianiline (6PFDA) [ka]

[0073] In a round-bottom flask (300 mL), 4-iodoacetanilide (18.49 g, 70.8 mmol), 1,6-diiodoperfluorohexane (21.58 g, 38.9 mmol), and dimethyl sulfoxide (DMSO, 90 mL) were dissolved. Copper powder (22.51 g, 354 mmol) was added, and the reaction was carried out at 120°C under a nitrogen stream for 24 hours. After the reaction, the mixture was cooled to room temperature, and the copper powder was removed by suction filtration. THF and saline solution were added to the filtrate, and the THF layer was collected. After dehydration with anhydrous sodium sulfate, the THF was removed by distillation to obtain a light brown product (6PFDAC). This was recrystallized in a THF / hexane mixed solvent to obtain white needle-shaped crystals. The yield was 9.8 g (yield: 50%). The melting point was 212-213°C. 1 H-NMR (DMSO-d6,ppm): 10.30(s,2H,NH), 7.78(d,4H,ArH), 7.56(d,4H,ArH), 2.08(s,6H,CH3). 19 F-NMR(DMSO-d6,ppm):-108.9, -121.2, -121.7 FT-IR(KBr,cm -1):3308(NH), 1681(C=O), 1183-1106(CF) In a round-bottom flask (500 mL), 6PFDAC (9.77 g, 17.2 mmol) and ethanol (180 mL) were added, and concentrated hydrochloric acid (31 mL) was added. The mixture was stirred at 100 °C for 1 hour under a nitrogen stream. After cooling to room temperature, distilled water (100 mL) was added and neutralized with sodium bicarbonate. Methylene chloride was added to the reaction solution, and the organic layer was recovered. Anhydrous sodium sulfate was added to the organic layer for dehydration. Methylene chloride was removed by distillation to obtain a pale yellow product (6PFDA). This was recrystallized on hexane to obtain pale yellow needle-shaped crystals. The yield was 5.4 g (yield: 65%), and the melting point was 78-79 °C. 1 H-NMR (DMSO-d6,ppm):7.21(s,4H,ArH), 6.65(s,4H,ArH), 5.85(s,4H,NH) 13 C-NMR(DMSO-d6,ppm):152.4, 127.8, 113.1 19 F-NMR(DMSO-d6,ppm):-107.5, -121.1, -121.7 FT-IR(KBr,cm -1 ):3444(NH), 3057(Ar-H), 1185(CF) Elemental analysis (C 18 H 12 N2F 12 ): Calculated values: C, 44.60%; H, 2.50%; N, 5.78% Measured values: C, 44.53%; H, 2.46%; N, 5.65%

[0074] <Synthesis Example 2> Synthesis of 4,4'-(1,6-perfluorohexylene)diphthalic anhydride (6PFDAH) [ka] In a round-bottom flask (100 mL), 4-iodo-o-xylene (10.0 g, 43 mmol), 1,6-diiodoperfluorohexane (13.6 g, 24 mmol), and DMSO (28 mL) were dissolved. Then, copper powder (13.9 g, 219 mmol) was added, and the mixture was reacted at 120°C under a nitrogen stream for 24 hours. After the reaction, the mixture was cooled to room temperature, t-butyl methyl ether was added to dissolve the product, and the copper powder was removed by suction filtration. Distilled water was added to the filtrate, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, t-butyl methyl ether was removed by distillation to obtain a white product (6BFBOX). This was recrystallized with methanol, and white needle-shaped crystals were obtained. The yield was 8.5 g, the yield was 77%, and the melting point was 84-85°C. 1 H-NMR(CDCl3,ppm):7.33(s,2H,ArH), 7.31(d,2H,ArH), 7.23(d,2H,ArH), 2.31(s,12H,CH3) 13 C-NMR(CDCl3,ppm):140.9, 137.1, 129.8, 127.8, 126.8, 124.4, 19.8 19 F-NMR(CDCl3,ppm):-132.2, -122.7, -111.6 FT-IR(KBr,cm -1 ):2944(CH), 2924(CH), 1222(CF), 1130(CF) Elemental analysis (C 22 H 18 F 12 ): Calculated values ​​C, 51.77%; H, 3.56% Measured values: C, 51.53%; H, 3.58% In a round-bottom flask (500 mL), 6PFBOX (4.0 g, 7.8 mmol), t-butyl alcohol (40 mL), and distilled water (160 mL) were added and stirred. KMnO4 (30.4 g, 192 mmol) was added at room temperature, and the reaction was carried out at 85 °C for 1 hour, followed by a reaction at 100 °C for 48 hours. After the reaction, the mixture was cooled to room temperature, and a saturated aqueous solution of sodium bicarbonate (8.1 g, 96 mmol) was added to the reaction solution and stirred for 30 minutes. The reaction solution was filtered through Celite, and concentrated hydrochloric acid was added to the filtrate to acidify the white product. t-butyl methyl ether (100 mL) was added and stirred for 1 hour to dissolve the product in the organic layer, and the organic layer was recovered. The organic layer was washed with saline solution until neutral. The organic layer was dehydrated with anhydrous sodium sulfate, and the t-butyl methyl ether was removed by distillation to obtain a white product (6PFBPA). This was recrystallized in a mixed solvent of distilled water / acetone, yielding white needle-shaped crystals. The yield was 3.8 g (yield: 77%), and the melting point was 207-208°C. 1 H-NMR (DMSO-d6,ppm): 13.6(br,4H,OH), 7.94-7.93(m,4H,ArH), 7.89(d,2H,ArH) 13 C-NMR(DMSO-d6,ppm):168.0, 167.0, 137.6, 132.9, 129.7, 129.4, 129.3, 126.8 19 F-NMR(DMSO-d6,ppm):-111.6, -122.7, -123.2 FT-IR(KBr,cm -1 ):3114(OH), 1736(C=O), 1222(CF), 1135(CF) Elemental analysis (C 22 H 10 O8F 12 ): Calculated values ​​C, 41.92%; H, 1.60% Measured values: C, 41.72%; H, 1.78% In a round-bottom flask (100 mL), 3.5 g (5.6 mmol) of 6PFBPA and 18 mL of acetic anhydride were added and stirred at 140 °C for 15 hours under a nitrogen stream. After the reaction, the acetic anhydride was removed under reduced pressure to obtain a pale yellow product. This was recrystallized in a mixed solvent of dehydrated ethyl acetate and dehydrated hexane to obtain pale brown needle-shaped crystals, which were further purified by sublimation (185 °C / 0.2 Torr) to obtain white powdery crystals (6PFDAH). The yield was 1.9 g (yield: 58%), and the melting point was 190-191 °C. 1 H-NMR(CDCl3,ppm):8.27(s,2H,ArH), 8.21(d,2H,ArH), 8.15(d,2H,ArH) 13 C-NMR(CDCl3,ppm):161.4, 161.3, 134.8, 134.4, 132.0, 126.4, 124.8 19 F-NMR(CDCl3,ppm):-112.1, -122.3, -122.5 FT-IR(KBr,cm -1 ):3140~3010(Ar-H), 1862(C=O), 1798(C=O), 1134(CF) Elemental analysis (C 22 H6O6F 12 ): Calculated values ​​C, 44.46%; H, 1.02% Measured values: C, 44.28%; H, 1.16%

[0075] <Synthesis Example 3> Synthesis of 4,4'-(1,4-perfluorobutylene)diphthalic anhydride (4PFDAH) [ka]

[0076] In a round-bottom flask (100 mL), 4-iodo-o-xylene (10.0 g, 43 mmol), 1,4-diiodoperfluorobutane (10.8 g, 24 mmol), 2,2'-bipyridyl (1.35 g, 8.6 mmol), and DMSO (30 mL) were dissolved. Then, copper powder (13.7 g, 215 mmol) was added, and the reaction was carried out at 70°C under a nitrogen stream for 48 hours. After the reaction, the mixture was cooled to room temperature, t-butyl methyl ether was added to the reaction solution, and the copper powder was removed by suction filtration. The filtrate was washed with distilled water, and the organic layer was recovered. Anhydrous sodium sulfate was added to the organic layer to dehydrate it, and the t-butyl methyl ether was removed by distillation to obtain the crude product. This was recrystallized in a methanol / distilled water mixed solvent to obtain white needle-shaped crystals (4PFBOX). The yield was 3.7 g (yield: 42%), and the melting point was 89-90°C. 1 H-NMR(CDCl3,ppm):7.32(s,2H,ArH), 7.30(d,2H,ArH), 7.21(d,2H,ArH), 2.30(s,12H,CH3) FT-IR(KBr,cm -1 ):2927(CH), 1177(CF), 1121(CF) In a round-bottom flask (500 mL), 4PFBOX (3.5 g, 8.5 mmol), t-butyl alcohol (35 mL), and distilled water (175 mL) were added and stirred to form a suspension. KMnO4 (32.3 g, 204 mmol) was added to this suspension, and the mixture was stirred at 80°C for 48 hours. The reaction solution was filtered through Celite, and concentrated hydrochloric acid was added to the filtrate to acid precipitate the white product. t-butyl methyl ether (100 mL) was added, and the mixture was stirred for 1 hour to dissolve the product in the organic layer. The organic layer was collected and washed with brine until the organic layer was neutral. The organic layer was dehydrated with anhydrous sodium sulfate, and the t-butyl methyl ether was removed by distillation to obtain a white product. This was recrystallized in a mixed solvent of distilled water / acetone to obtain white needle-shaped crystals (4PFBPA). The yield was 3.0 g, the yield was 66%, and the melting point was 204-205°C. 1 H-NMR (DMSO-d6,ppm): 13.6(br,4H,OH), 7.90~7.92(m,4H,ArH), 7.86(d,2H,ArH) FT-IR(KBr,cm -1 ):3200~2900(OH), 1736(C=O), 1116(CF) In a round-bottom flask (100 mL), 4PFBPA (2.9 g, 5.5 mmol) and acetic anhydride (15 mL) were added and reacted at 140°C for 15 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, and the acetic anhydride was removed under reduced pressure to obtain a light brown product. This was recrystallized in a mixed solvent of dehydrated ethyl acetate / hexane to obtain light brown needle-shaped crystals, and further sublimation purification (195°C / 0.2 Torr) yielded white powdery crystals (4PFDAH). The yield was 1.6 g, with a yield of 58%, and the melting point was 199-200°C. 1 H-NMR(CDCl3,ppm):8.25(s,2H,ArH), 8.20(d,2H,ArH), 8.15(d,2H,ArH) FT-IR(KBr,cm -1 ):3067(Ar-H), 1860(C=O), 1797(C=O), 1118(CF)

[0077] <Example 1> Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDA-6PFDAH) [ka] In a round-bottom flask (100 mL) fitted with a stirring rod, nitrogen inlet tube, and Liebig condenser, 6PFDA (0.726 g, 1.50 mmol) and anhydrous NMP (3 mL) were added and dissolved. To this solution, 6PFDAH (0.891 g, 1.50 mmol) was added and dissolved while stirring at room temperature. After stirring at 60°C for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η) of the fluorinated polyamide compound was then measured. inhThe concentration was 0.34 dL / g (0.5 g / dL NMP solution, measured at 30°C). An NMP solution (20 wt%) of the fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Subsequently, a pale yellow, translucent fluorinated polyimide compound (6PFDA-6PFDAH) film (thickness 40 μm) was prepared by stepwise heating in a vacuum dryer at 60°C for 6 hours, 100°C for 1 hour, 200°C for 1 hour, and 250°C for 1 hour. The properties of the obtained fluorinated polyimide compound film are shown below. FT-IR (film, cm) -1 ):1785(C=O), 1723(C=O), 1380(CN), 1200(CF), 720(CN) Solubility: Insoluble in organic solvents such as NMP, DMAc, DMF, DMI, THF, and chloroform. Temperature at which weight loss of 5% occurs: 529°C (in air), 538°C (in nitrogen). Temperature at which weight loss of 10% occurs: 544°C (in air), 554°C (in nitrogen). Carbonization yield: 46% (in nitrogen, 800°C) Glass transition temperature: 159°C (measured by DSC) Melting point: 350°C (measured by DSC) Cutoff wavelength: 372nm Transmittance at 500nm: 27% Average refractive index (n ave ):1.538(d line) Permittivity (ε) calculated from refractive index: 2.60 (ε = 1.10 × n) ave 2 ) Dielectric constant (D k ):2.56(TM, 10GHz), 2.48(TE, 20GHz) Dielectric loss tangent (D f ):0.0015(TM, 10GHz), 0.0016(TE, 20GHz)

[0078] <Example 2> Fluorinated polyamide compounds and fluorinated polyimide compounds (BisAAF-6PFDAH) [ka] BisAAF (0.501 g, 1.50 mmol) and anhydrous NMP (3 mL) were added to a round-bottom flask (100 mL) fitted with a stirring rod, nitrogen inlet tube, and Liebig condenser, and dissolved. 6PFDAH (0.891 g, 1.50 mmol) was added to this solution and dissolved while stirring at room temperature. After stirring at 60°C for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η) of the fluorinated polyamide compound was then measured. inh The concentration was 0.34 dL / g (0.5 g / dL NMP solution, measured at 30°C). An NMP solution (20 wt%) of the fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Subsequently, a pale yellow, transparent film (thickness 29 μm) of the fluorinated polyimide compound (BisAAF-6PFDAH) was prepared by stepwise heating in a vacuum dryer at 60°C for 6 hours, 100°C for 1 hour, 200°C for 1 hour, and 250°C for 1 hour. The properties of the obtained fluorinated polyimide compound film are shown below. FT-IR (film, cm) -1 ):1787(C=O), 1729(C=O), 1376(CN), 1207(CF), 719(CN) Solubility: Soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidone (DMI), tetrahydrofuran (THF), γ-butyrolactone, and chloroform. Logarithmic viscosity (η inh ): 0.38 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Number average molecular weight (M n ): 30,000 Weight average molecular weight (M w ): 87,000 Molecular weight distribution (M w / M n ):3.0 Temperature at which weight loss of 5% occurs: 513°C (in air), 526°C (in nitrogen). 10% weight loss temperature: 533 °C (in air), 545 °C (in nitrogen) Carbonization yield: 52% (in nitrogen, 800 °C) Glass transition temperature: 207 °C (DSC measurement), 213 °C (DMA measurement), 207 °C (TMA measurement) Coefficient of thermal expansion (CTE): 81 ppm / °C (temperature range from 100 °C to 150 °C, TMA measurement) Cut-off wavelength: 341 nm Transmittance at 500 nm: 81% Average refractive index (n ave ): 1.525 (d line) Dielectric constant (ε) calculated from refractive index: 2.56 (ε = 1.10 × n ave 2 ) Dielectric constant (D k ): 2.53 (TE, 10 GHz), 2.53 (TM, 10 GHz), 2.53 (TE, 20 GHz) Dielectric tangent (D f ): 0.0026 (TE, 10 GHz), 0.0030 (TM, 10 GHz), 0.0031 (TE, 20 GHz)

[0079] <Example 3> Fluorinated polyamide compound and fluorinated polyimide compound (6PFDA / BisAAF(50 / 50)-6PFDAH)

Chemical formula

[0080] <Example 4> Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDA-6PFDAH / 6FDA(50 / 50)) [ka] In a round-bottom flask (100 mL) fitted with a stirring rod, nitrogen inlet tube, and Liebig condenser, 6PFDA (0.726 g, 1.50 mmol) and anhydrous NMP (3 mL) were added and dissolved. To this solution, 6PFDAH (0.446 g, 0.75 mmol) and 6FDA (0.333 g, 0.75 mmol) were added and dissolved while stirring at room temperature. After stirring at 60°C for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η) of the fluorinated polyamide compound was then measured. inh The concentration was 0.33 dL / g (0.5 g / dL NMP solution, measured at 30°C). An NMP solution (20 wt%) of the fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Subsequently, a pale yellow, transparent film (thickness 34 μm) of the fluorinated polyimide compound (6PFDA-6PFDAH / 6FDA(50 / 50)) was prepared by stepwise heating in a vacuum dryer at 60°C for 6 hours, 100°C for 1 hour, 200°C for 1 hour, and 250°C for 1 hour. The properties of the obtained fluorinated polyimide compound film are shown below. FT-IR (film, cm) -1 ):1787(C=O), 1727(C=O), 1372(CN), 1194(CF), 720(CN) Solubility: Insoluble in organic solvents such as NMP, DMAc, DMF, DMI, γ-butyrolactone, THF, and chloroform. Temperature at which weight loss of 5% occurs: 507°C (in air), 524°C (in nitrogen). Temperature at which weight loss of 10% occurs: 522°C (in air), 542°C (in nitrogen). Carbonization yield: 45% (in nitrogen, 800°C) Glass transition temperature: 191°C (DSC measurement), 184°C (DMA measurement), 187°C (TMA measurement) Coefficient of thermal expansion (CTE): 103 ppm / °C (temperature range of 100°C to 150°C, TMA measurement) Cutoff wavelength: 363nm (UV-vis) Transmittance at 500nm: 65% (UV-vis) Average refractive index (n ave ):1.517(d line) Permittivity (ε) calculated from refractive index: 2.53 (ε = 1.10 × n) ave 2 ) Dielectric constant (D k ):2.48(TE, 10GHz), 2.49(TM, 10GHz), 2.49(TE, 20GHz) Dielectric loss tangent (D f ):0.0017(TE, 10GHz), 0.0014(TM, 10GHz), 0.0019(TE, 20GHz)

[0081] <Example 5> Fluorinated polyamide compounds and fluorinated polyimide compounds (BisAAF-4PFDAH) [ka] BisAAF (0.501 g, 1.50 mmol) and anhydrous NMP (3 mL) were added to a round-bottom flask (100 mL) fitted with a stirring rod, nitrogen inlet tube, and Liebig condenser, and dissolved. 4PFDAH (0.741 g, 1.50 mmol) was added to this solution and dissolved while stirring at room temperature. After stirring at 30°C for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η) of the fluorinated polyamide compound was then measured. inh The concentration was 0.37 dL / g (0.5 g / dL NMP solution, measured at 30°C). An NMP solution (20 wt%) of the fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Subsequently, a pale yellow, transparent film (thickness 32 μm) of the fluorinated polyimide compound (BisAAF-4PFDAH) was prepared by stepwise heating in a vacuum dryer at 60°C for 6 hours, 100°C for 1 hour, 200°C for 1 hour, and 250°C for 1 hour. The properties of the obtained fluorinated polyimide compound film are shown below. FT-IR (film, cm) -1 ):1787(C=O), 1729(C=O), 1376(CN), 1207(CF), 719(CN) Logarithmic viscosity (η inh ): 0.56 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Number average molecular weight (M n ): 38,000 Weight average molecular weight (M w ): 114,000 Molecular weight distribution (M w / M n ):3.0 Solubility: Soluble in organic solvents such as NMP, DMAc, DMF, DMI, γ-butyrolactone, THF, and chloroform. Temperature at which weight loss of 5% occurs: 504°C (in air), 529°C (in nitrogen). Temperature at which weight loss of 10% occurs: 522°C (in air), 545°C (in nitrogen). Carbonization yield: 52% (in nitrogen, 800°C) Glass transition temperature: 238°C (DSC measurement), 230°C (DMA measurement), 229°C (TMA measurement) Coefficient of thermal expansion (CTE): 77 ppm / °C (temperature range of 100°C to 150°C, TMA measurement) Average refractive index (n ave ):1.552(d line) Permittivity (ε) calculated from refractive index: 2.65 (ε = 1.10 × n) ave 2 ) Dielectric constant (D k ):2.57(TE, 10GHz), 2.52(TM, 10GHz), 2.55(TE, 20GHz) Dielectric loss tangent (D f ):0.0047(TE, 10GHz), 0.0045(TM, 10GHz), 0.0049(TE, 20GHz)

[0082] <Example 6> Fluorinated polyamide compounds and fluorinated polyimide compounds (m-6PFDA-6PFDAH) [ka] In Example 1, m-6PFDA was used instead of 6PFDA, and the mixture was stirred in dehydrated NMP at 60°C for 18 hours to obtain a viscous fluorinated polyamide compound. The logarithmic viscosity (η) of the fluorinated polyamide compound was then calculated. inh The concentration was 0.30 dL / g (0.5 g / dL NMP solution, measured at 30°C). This NMP solution of fluorinated polyamide compound was cast onto a glass plate, and the temperature was gradually increased to 250°C and heated at 250°C for 1 hour to produce a pale yellow, transparent fluorinated polyimide compound (m-6PFDA-6PFDAH) film (thickness 70 μm). The properties of the obtained fluorinated polyimide compound film are shown below. Temperature at which weight loss of 5% occurs: 549°C (in nitrogen) Temperature at which weight loss of 10% occurs: 568°C (in nitrogen) Carbonization yield: 49% (in nitrogen, 800°C) Glass transition temperature: 120°C (DSC measurement), 112°C (DMA measurement), 117°C (TMA measurement) Coefficient of thermal expansion (CTE): 101 ppm / °C (temperature range from 50°C to 80°C, TMA measurement) Dielectric constant (D k ):2.39(TE, 10GHz), 2.43(TM, 10GHz), 2.35(TE, 20GHz) Dielectric loss tangent (D f ):0.0019(TE, 10GHz), 0.0021(TM, 10GHz), 0.0017(TE, 20GHz)

[0083] <Example 7> Fluorinated polyamide compounds and fluorinated polyimide compounds (TFMB-6PFDAH) [ka] In Example 2, TFMB was used instead of BisAAF, and the mixture was stirred in dehydrated NMP at room temperature for 18 hours to obtain a viscous fluorinated polyamide compound. The logarithmic viscosity (η) of the fluorinated polyamide compound was then calculated. inhThe concentration was 0.82 dL / g (0.5 g / dL NMP solution, measured at 30°C). This NMP solution of fluorinated polyamide compound was cast onto a glass plate, and the temperature was gradually increased to 250°C and heated at 250°C for 1 hour to produce a pale yellow, transparent fluorinated polyimide compound (TFMB-6PFDAH) film (thickness 55 μm). The properties of the obtained fluorinated polyimide compound film are shown below. Temperature at which weight loss of 5% occurs: 553°C (in nitrogen) Temperature at which weight loss of 10% occurs: 570°C (in nitrogen) Carbonization yield: 52% (in nitrogen, 800°C) Glass transition temperature: 211°C (DSC measurement), 209°C (TMA measurement) Coefficient of thermal expansion (CTE): 82 ppm / °C (temperature range of 140°C to 180°C, TMA measurement) Cutoff wavelength: 359nm (UV-vis) Transmittance at 500nm: 78% (UV-vis) Dielectric constant (D k ):2.47(TE, 10GHz), 2.59(TM, 10GHz), 2.51(TE, 20GHz) Dielectric loss tangent (D f ):0.0017(TE, 10GHz), 0.0018(TM, 10GHz), 0.0021(TE, 20GHz)

[0084] <Example 8> Fluorinated polyamide compounds and fluorinated polyimide compounds (BAFL-6PFDAH) [ka] In Example 2, BAFL was used instead of BisAAF, and the mixture was stirred in dehydrated NMP at room temperature for 18 hours to obtain a viscous fluorinated polyamide compound. The logarithmic viscosity (η) of the fluorinated polyamide compound was then calculated. inhThe concentration was 0.43 dL / g (0.5 g / dL NMP solution, measured at 30°C). This NMP solution of fluorinated polyamide compound was cast onto a glass plate, and the temperature was gradually increased to 300°C and heated at 300°C for 1 hour to produce a pale yellow, transparent fluorinated polyimide compound (BAFL-6PFDAH) film (thickness 60 μm). The properties of the obtained fluorinated polyimide compound film are shown below. Solubility: Soluble in organic solvents such as NMP, DMAc, DMF, TMU, DMI, DMSO, γ-butyrolactone, THF, and chloroform. Temperature at which weight loss of 5% occurs: 528°C (in nitrogen) Temperature at which weight loss of 10% occurs: 547°C (in nitrogen) Glass transition temperature: 272°C (DSC measurement), 263°C (DMA measurement), 274°C (TMA measurement) Coefficient of thermal expansion (CTE): 80 ppm / °C (temperature range of 150°C to 200°C, TMA measurement) Cutoff wavelength: 365nm (UV-vis) Transmittance at 500nm: 86% (UV-vis) Average refractive index (n ave ):1.591(d line) Permittivity (ε) calculated from refractive index: 2.78 (ε = 1.10 × n) ave 2 ) Dielectric constant (D k ):2.61(TE, 10GHz), 2.68(TM, 10GHz), 2.59(TE, 20GHz) Dielectric loss tangent (D f ):0.0020(TE, 10GHz), 0.0022(TM, 10GHz), 0.0023(TE, 20GHz)

[0085] <Example 9> Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDA-4PFDAH) [ka] In Example 5, 6PFDA was used instead of BisAAF, and the mixture was stirred in dehydrated NMP at 60°C for 18 hours to obtain a viscous fluorinated polyamide compound. The logarithmic viscosity (η) of the fluorinated polyamide compound was then calculated. inh The concentration was 0.38 dL / g (0.5 g / dL NMP solution, measured at 30°C). This NMP solution of fluorinated polyamide compound was cast onto a glass plate, and the temperature was gradually increased to 250°C and heated at 250°C for 1 hour to produce a pale yellow, translucent fluorinated polyimide compound (6PFDA-4PFDAH) film (thickness 80 μm). The properties of the obtained fluorinated polyimide compound film are shown below. Temperature at which weight loss of 5% occurs: 532°C (in air), 529°C (in nitrogen). Temperature at which weight loss of 10% occurs: 549°C (in air), 545°C (in nitrogen). Carbonization yield: 52% (in nitrogen, 800°C) Melting point: 330°C (measured by DSC) Average refractive index (n ave ):1.551(d line) Permittivity (ε) calculated from refractive index: 2.65 (ε = 1.10 × n) ave 2 ) Dielectric constant (D k ):2.53(TM, 10GHz) Dielectric loss tangent (D f ):0.0025(TM, 10GHz)

[0086] <Comparative Example 1> Fluorinated polyamide compounds and fluorinated polyimide compounds (BisAAF-6FDA) [ka] BisAAF (0.501 g, 1.50 mmol) and anhydrous NMP (3 mL) were added to a round-bottom flask (100 mL) fitted with a stirring rod, nitrogen inlet tube, and Liebig condenser, and dissolved. 6FDA (0.666 g, 1.50 mmol) was added to this solution and dissolved while stirring at room temperature. After stirring at 60°C for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η) of the fluorinated polyamide compound was then measured. inh The concentration was 0.58 dL / g (0.5 g / dL NMP solution, measured at 30°C). An NMP solution (20 wt%) of the fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Subsequently, a pale yellow, transparent film (thickness 58 μm) of the fluorinated polyimide compound (BisAAF-6FDA) was prepared by stepwise heating in a vacuum dryer at 60°C for 6 hours, 100°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, and 300°C for 1 hour. The properties of the obtained fluorinated polyimide compound film are shown below. FT-IR (film, cm) -1 ):1790(C=O), 1730(C=O), 1380(CN), 1210(CF), 720(CN) Number average molecular weight (M n ):26,000 Weight average molecular weight (M w ): 61,000 Molecular weight distribution (M w / M n ):2.3 Solubility: Soluble in NMP, DMAc, DMF, DMI, γ-butyrolactone, THF, and chloroform. Temperature at which weight loss of 5% occurs: 508°C (in air), 524°C (in nitrogen). Temperature at which weight loss of 10% occurs: 525°C (in air), 539°C (in nitrogen). Carbonization yield: 54% (in nitrogen, 800°C) Glass transition temperature: 311°C (DSC measurement), 313°C (DMA measurement), 310°C (TMA measurement) Coefficient of thermal expansion (CTE): 69 ppm / °C (temperature range of 100°C to 150°C, TMA measurement) Cutoff wavelength: 354nm Transmittance at 500nm: 88% Average refractive index (n ave ):1.550(d line) Permittivity (ε) calculated from refractive index: 2.64 (ε = 1.10 × n) ave 2 ) Dielectric constant (D k ):2.65(TE, 10GHz), 2.63(TM, 10GHz), 2.59(TE, 20GHz) Dielectric loss tangent (D f ):0.0070(TE, 10GHz), 0.0053(TM, 10GHz), 0.0044(TE, 20GHz)

Claims

1. A fluorinated polyamide compound having repeating units shown in formula (1). Formula (1): [Chemistry 18] (In formula (1), n ​​is an integer from 1 to 8, ring A and ring B are independently substituted or unsubstituted hydrocarbon rings, R is independently H, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, L is a structure represented by the following formula (3) (in formula (3) below, * indicates the bond position with ring A), R １ (Each represents independently an OH group, a optionally substituted linear or branched alkoxy group, an optionally substituted aromatic oxy group, or a halogen atom.) Formula (3): 【Chemistry 22】

2. The fluorinated polyamide compound according to claim 1, wherein ring A is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring.

3. The fluorinated polyamide compound according to claim 1 or 2, wherein ring B is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring.

4. The fluorinated polyamide compound according to claim 1 or 2, wherein the repeating unit represented by formula (1) is the repeating unit represented by formula (1-1). Formula (1-1): 【Chemistry 19】 (In formula (1-1), n, L and R １ (As stated above.)

5. A fluorinated polyimide compound having repeating units shown in formula (2). Formula (2): 【Chemistry 20】 (In formula (2), n is an integer from 1 to 8, ring A and ring B are independently substituted or unsubstituted hydrocarbon rings, R is independently H, a linear, branched or cyclic aliphatic group, a substituted or unsubstituted aromatic group, a linear, branched or cyclic fluorinated aliphatic group, or a substituted or unsubstituted fluorinated aromatic group, and L represents the structure shown in formula (3) below (where * indicates the bond position with ring A).) Formula (3): 【Chemistry 23】

6. The fluorinated polyimide compound according to claim 5, wherein ring A is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring.

7. The fluorinated polyimide compound according to claim 5 or 6, wherein ring B is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a phenanthrene ring, an anthracene ring, or a terphenyl ring.

8. The fluorinated polyimide compound according to claim 5 or 6, wherein the repeating unit shown in formula (2) is the repeating unit shown in formula (2-1). Formula (2-1): 【Chemistry 21】 (In equation (2-1), n ​​and L are as described above.)

9. The fluorinated polyimide compound according to claim 5 or 6, wherein the dielectric loss tangent (Df) at 10 GHz is 0.005 or less.

10. A low-dielectric material containing a fluorinated polyamide compound according to claim 1 or 2, or a fluorinated polyimide compound according to claim 5 or 6.

11. A high-frequency electronic component containing a fluorinated polyamide compound according to claim 1 or 2, or a fluorinated polyimide compound according to claim 5 or 6.

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