Fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles

Abstract

The present invention provides: a fluorine-containing polyamide compound which has specific repeating units; and a fluorine-containing polybenzoxazole which has specific repeating units.

Description

[Technical Field]

[0001] This disclosure relates to fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles. [Background technology]

[0002] Polybenzoxazole resins, like polyimide resins, are resins with excellent heat resistance and mechanical properties, and are used as interlayer insulating films and protective films for semiconductors, interlayer insulating films for multilayer circuits, cover coats for flexible wiring boards, and solder resists. To apply these to electrical and electronic materials, a method for producing polyhydroxyamide, a high-purity polybenzoxazole precursor free of ionic impurities, has been proposed (Patent Documents 1 and 2).

[0003] Patent Document 2 contains the following formula (A) [ka] The present invention describes a polybenzoxazole precursor resin obtained by a polymerization reaction between a dicarboxylic acid triazine active ester represented by formula (A), where R1 represents a divalent aromatic residue containing one or more elements selected from O, N, S, F, and Si in its structure, or a divalent organic group having 1 to 12 carbon atoms; and R2 represents an alkyl group having 1 to 4 carbon atoms or an aromatic residue having 6 to 8 carbon atoms, wherein the polybenzoxazole precursor resin has a weight-average molecular weight in the range of 10,000 to 1,000,000 and an ionic impurity content of 10 ppm or less.

[0004] Furthermore, fluorinated polybenzoxazoles containing fluorine atoms with low polarizability have been reported for applications such as printed circuit boards (Patent Documents 3, 4, and 5).

[0005] However, there is a demand for polybenzoxazole resins that possess low dielectric constant, low dielectric loss tangent, and good moldability, enabling them to be used in high-frequency printed circuit boards. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-183846 [Patent Document 2] Japanese Patent Publication No. 2011-256219 [Patent Document 3] Japanese Patent Publication No. 2000-212281 [Patent Document 4] Japanese Patent Publication No. 2000-219742 [Patent Document 5] Japanese Patent Publication No. 2006-45321 [Overview of the project] [Problems that the invention aims to solve]

[0007] The object of this disclosure is to provide a highly soluble fluorine-containing polyamide compound that can produce a fluorine-containing polybenzoxazole with a low dielectric constant and low dielectric loss tangent, suitable for use with high-frequency printed circuit boards. Furthermore, this disclosure aims to provide a fluorine-containing polybenzoxazole with a low dielectric constant and low dielectric loss tangent, suitable for use with high-frequency printed circuit boards. [Means for solving the problem]

[0008] The present disclosure provides a fluorine-containing polyamide compound having repeating units represented by formula (1). Formula (1): [ka] (In formula (1), n ​​is an integer from 1 to 8, L is a linking group, and rings A and B independently represent hydrocarbon rings.)

[0009] In formula (1), it is preferable that ring A is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, or a terphenyl ring. In formula (1), it is preferable that ring B is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, or a terphenyl ring. In formula (1), it is preferable that the linking group is a single bond, -SO2-, -O-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group. It is preferable that the repeating unit shown in formula (1) is the repeating unit shown in formula (1-1). Formula (1-1): [ka] (In equation (1-1), n ​​and L are as described above.) It is preferable that the average degree of polymerization of the repeating units shown in formula (1) is between 2 and 100.

[0010] Furthermore, this disclosure provides a fluorine-containing polybenzoxazole having repeating units represented by formula (2). Formula (2): [ka] (In formula (2), n is an integer from 1 to 8, L is a linking group, and rings A and B independently represent hydrocarbon rings.)

[0011] In formula (2), it is preferable that ring A is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, or a terphenyl ring. In formula (2), it is preferable that ring B is a cyclohexane ring, a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, or a terphenyl ring. In formula (2), it is preferable that the linking group is a single bond, -SO2-, -O-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group. It is preferable that the repeating unit shown in formula (2) is the same as the repeating unit shown in formula (2-1). Formula (2-1): [ka] (In equation (2-1), n ​​and L are as described above.) It is preferable that the average degree of polymerization of the repeating units shown in formula (2) is between 2 and 100.

[0012] Furthermore, this disclosure provides a low-dielectric material containing the above-mentioned fluorine-containing polyamide compound or the above-mentioned fluorine-containing polybenzoxazole.

[0013] Furthermore, this disclosure provides an insulating material for a printed circuit board containing the above-mentioned fluorine-containing polyamide compound or the above-mentioned fluorine-containing polybenzoxazole. [Effects of the Invention]

[0014] According to this disclosure, it is possible to provide a highly soluble fluorine-containing polyamide compound that can be obtained from a fluorine-containing polybenzoxazole with a low dielectric constant and a low dielectric loss tangent. Furthermore, this disclosure makes it possible to provide a fluorine-containing polybenzoxazole with a low dielectric constant and a low dielectric loss tangent. [Modes for carrying out the invention]

[0015] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.

[0016] <Fluorine-containing polyamide compounds> The fluorine-containing polyamide compounds of this disclosure have repeating units represented by formula (1).

[0017] Formula (1): [ka] (In formula (1), n ​​is an integer from 1 to 8, L is a linking group, and rings A and B independently represent hydrocarbon rings.)

[0018] n represents an integer between 1 and 8. Preferably, n is an integer between 4 and 8, and more preferably 4, 6, or 8.

[0019] L represents a linking group. Preferred linking groups are single bonds, -SO2-, -O-, -CO-, divalent non-fluorinated organic groups, or divalent fluorinated organic groups; more preferred are single bonds, -O-, divalent non-fluorinated organic groups, or divalent fluorinated organic groups; even more preferred are divalent non-fluorinated organic groups or divalent fluorinated organic groups; and particularly preferred are divalent fluorinated organic groups.

[0020] 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.

[0021] The above-mentioned fluorinated organic group is a divalent organic group having one or more fluorine atoms. A linear or branched fluorinated alkylene group is preferred for L.

[0022] As the fluorinated alkylene group mentioned above, a perfluoroalkylene group is preferred.

[0023] The number of carbon atoms in the above-mentioned fluorinated alkylene group is preferably 1 to 15, more preferably 2 or more, more preferably 10 or less, and even more preferably 6 or less, in order to lower the dielectric constant and dielectric loss tangent of the fluorinated polyamide compound and further increase its solubility.

[0024] The preferred fluorinated alkylene group is -C(CF3)2-.

[0025] Rings A and B independently represent hydrocarbon rings. A hydrocarbon ring may be monocyclic or polycyclic, and may be aliphatic or aromatic hydrocarbon ring. An aliphatic hydrocarbon ring may be a saturated or unsaturated hydrocarbon ring that does not possess aromaticity.

[0026] The carbonyl group and difluoromethylene group adjacent to the hydrocarbon ring of ring A are not particularly limited in their positions when bonded to the hydrocarbon ring; they can bond to any carbon atom among the carbon atoms constituting the hydrocarbon ring.

[0027] The number of carbon atoms in ring A is preferably 3 to 30, more preferably 5 or more, even more preferably 6 or more, more preferably 20 or less, and even more preferably 18 or less.

[0028] The hydrocarbon ring of ring A may or may not have substituents. Examples of substituents include halogen atoms such as fluorine atoms, alkyl groups such as methyl groups, alkyl halides such as trifluoromethyl groups, and aryl groups such as phenyl groups.

[0029] As for ring A, Monocyclic saturated hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane rings; Monocyclic non-aromatic unsaturated hydrocarbon rings such as cyclopropene rings, cyclobutene rings, cyclohexene rings, cycloheptene rings, and cyclooctene rings; Polycyclic non-aromatic hydrocarbon rings such as norbornene rings, norbornadiene rings, decahydronaphthalene rings, bicycloundecane rings, and spirobicyclopentane rings; Aromatic hydrocarbon rings such as benzene rings, naphthalene rings, phenanthrene rings, anthracene rings, fluorene rings, tetracene rings, chrysene rings, pyrene rings, pentacene rings, benzopyrene rings, triphenylene rings, biphenyl rings, terphenyl groups, diphenylmethane rings, diphenyl ether rings, diphenyl sulfone rings, and diphenyl ketone rings; These are some examples.

[0030] Among the rings A, benzene rings, naphthalene rings, anthracene rings, biphenyl rings, or terphenyl rings are preferred, with benzene rings being more preferred. These rings may or may not have substituents.

[0031] The positions in which the amino group adjacent to the hydrocarbon ring of ring B and the linking group of L bond to the hydrocarbon ring are not particularly limited; they can bond to any carbon atom among the carbon atoms constituting the hydrocarbon ring.

[0032] The number of carbon atoms in ring B is preferably 3 to 30, more preferably 5 or more, even more preferably 6 or more, even more preferably 20 or less, and even more preferably 18 or less.

[0033] The hydrocarbon ring of ring B may or may not have substituents. Examples of substituents include halogen atoms such as fluorine atoms, alkyl groups such as methyl groups, alkyl halides such as trifluoromethyl groups, and aryl groups such as phenyl groups.

[0034] As for ring B, Monocyclic saturated hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane rings; Monocyclic non-aromatic unsaturated hydrocarbon rings such as cyclopropene rings, cyclobutene rings, cyclohexene rings, cycloheptene rings, and cyclooctene rings; Polycyclic non-aromatic hydrocarbon rings such as norbornene rings, norbornadiene rings, decahydronaphthalene rings, bicycloundecane rings, and spirobicyclopentane rings; Aromatic hydrocarbon rings such as benzene rings, naphthalene rings, phenanthrene rings, anthracene rings, fluorene rings, tetracene rings, chrysene rings, pyrene rings, pentacene rings, benzopyrene rings, triphenylene rings, biphenyl rings, terphenyl groups, diphenylmethane rings, diphenyl ether rings, diphenyl sulfone rings, and diphenyl ketone rings; These are some examples.

[0035] Among the ring B components, a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, or a terphenyl ring is preferred, with a benzene ring being more preferred. These components may or may not have substituents.

[0036] The repeating unit shown in formula (1) is preferably the repeating unit shown in formula (1-1).

[0037] Formula (1-1): [ka] (In equation (1-1), n ​​and L are as described above.)

[0038] In the fluorine-containing polyamide compounds of this disclosure, the average degree of polymerization of the repeating units represented by formula (1) is preferably 200 or less, more preferably 150 or less, even more preferably 100 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 (Mn) of the fluorine-containing polyamide compounds of this disclosure.

[0039] The number-average molecular weight (Mn) of the fluorine-containing polyamide compounds of this disclosure is preferably 10,000 or more, more preferably 20,000 or more, preferably 1,000,000 or less, and more preferably 500,000 or less, based on standard polystyrene equivalent as determined by gel permeation chromatography (GPC).

[0040] The molecular weight distribution (Mw / Mn) of the fluorine-containing polyamide compounds of this disclosure is preferably 2 or more, preferably 5 or less, and more preferably 4 or less, based on standard polystyrene equivalents determined by gel permeation chromatography (GPC).

[0041] The logarithmic viscosity η of the fluorine-containing 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 fluorine-containing 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, and using the following formula. Logarithmic viscosity η inh = ln(solution viscosity / solvent viscosity) / solution concentration

[0042] The fluorine-containing polyamide compounds of this disclosure can be suitably used as precursors to fluorine-containing polybenzoxazoles having repeating units represented by formula (2), as described later.

[0043] <Fluorine-containing polybenzoxazole> The fluorine-containing polybenzoxazoles of this disclosure have repeating units represented by formula (2).

[0044] Formula (2): [ka] (In formula (2), n is an integer from 1 to 8, L is a linking group, and rings A and B independently represent hydrocarbon rings.)

[0045] n, L, ring A, and ring B in equation (2) are the same as n, L, ring A, and ring B in equation (1).

[0046] The repeating unit shown in formula (2) is preferably the repeating unit shown in formula (2-1).

[0047] Formula (2-1): [ka] (In equation (2-1), n ​​and L are as described above.)

[0048] The glass transition temperature of the fluorine-containing polybenzoxazoles 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).

[0049] In the fluorine-containing polybenzoxazole of this disclosure, the average degree of polymerization of the repeating units represented by formula (2) is preferably 200 or less, more preferably 100 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 (Mn) of the fluorine-containing polybenzoxazole of this disclosure. Since the dielectric constant and dielectric loss tangent of the fluorine-containing polybenzoxazole can be further reduced, the fluorine-containing polybenzoxazole may be a polymer with a relatively large average degree of polymerization, for example, a polymer with an average degree of polymerization of more than 100.

[0050] The number-average molecular weight (Mn) of the fluorine-containing polybenzoxazole of this disclosure is preferably 10,000 or more, more preferably 20,000 or more, preferably 1,000,000 or less, and more preferably 500,000 or less, based on standard polystyrene equivalent as determined by gel permeation chromatography.

[0051] The molecular weight distribution (Mw / Mn) of the fluorine-containing polybenzoxazoles of this disclosure is preferably 2 or more, preferably 5 or less, and more preferably 4 or less, based on standard polystyrene equivalent as determined by gel permeation chromatography.

[0052] The logarithmic viscosity η of the fluorine-containing polybenzoxazole of this disclosure 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 fluorine-containing polybenzoxazole 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 obtained solution at 30°C, and using the following formula. Logarithmic viscosity η inh = ln (solution viscosity / solvent viscosity) / solution concentration

[0053] <Method for Producing Fluorine-containing Polyamide Compound> The fluorine-containing polyamide compound of the present disclosure can be preferably produced by producing the fluorinated compound (3) represented by the formula (3) by the production method described later and then polymerizing the obtained fluorinated compound (3) with the compound (4) represented by the formula (4).

[0054] Formula (3):

Chemical formula

[0055] Formula (4):

Chemical formula

[0056] n and ring A in formula (3) are the same as n and ring A in formula (1).

[0057] R in formula (3) 1 independently represents 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.

[0058] R 1 The number of carbon atoms of the alkoxy group as R is preferably 1 to 12, more preferably 1 to 6.

[0059] R 1The substituents that the alkoxy group and aromatic oxy group may have are preferably alkoxy groups, alkyl groups, fluorinated alkyl groups, halo groups (halogen atoms), nitro groups, cyano groups, or ester groups, with alkoxy groups being more preferred.

[0060] R 1 Examples of aromatic oxy groups include phenoxy groups which may have substituents, and triazinyloxy groups which may have substituents.

[0061] R 1 These can be independently OH, a phenoxy group which may have substituents, a methoxy group, an ethoxy group, a chlorine atom, or [ka] It is preferable.

[0062] As the fluorinated compound (3), the compound represented by formula (3-1) is preferred. Formula (3-1): [ka] (In equation (3-1), n ​​and R 1 (As stated above.)

[0063] As the fluorinated compound (3), the compound represented by formula (3-1a) or formula (3-1b) is more preferred. Formula (3-1a): [ka] (In equation (3-1a), n and R 1 (As stated above.)

[0064] Formula (3-1b): [ka] (In equation (3-1b), n and R 1 (As stated above.)

[0065] L and ring B in equation (4) are the same as L and ring B in equation (1).

[0066] As the fluorinated compound (4), the compound represented by formula (4-1) is preferred. Formula (4-1): [ka] (In equation (4-1), L is as described above.)

[0067] Polymerization of fluorinated compound (3) and compound (4) can be carried out in a solvent. The solvent should not substantially react with fluorinated compound (3) and compound (4), and should have the property of dissolving fluorinated compound (3) and compound (4) well, and should also be a good solvent for the compound obtained by polymerization of fluorinated 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), dimethyl sulfone, sulfolane, tetrahydrofuran (THF), cyclopentanone, cyclohexanone, and acetone. Among these, N-methyl-2-pyrrolidone (NMP) and 1,3-dimethylimidazolidone (DMI) are preferred. The amount of these solvents used is usually 10 to 1000 mL, preferably 50 to 400 mL, per 0.1 mole of fluorinated compound (3) or compound (4).

[0068] 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. In addition, silylation agents such as trialkylsilyl chloride, N,O-bis(trimethylsilyl)acetamide (BSA), and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) may be added to obtain compounds with high molecular weight. Among these silylation agents, BSA is preferred. The amount of silylation agent added is preferably 4 times the molar amount of compound (4) or less, and more preferably 1 to 2 times the molar amount.

[0069] Polymerization can be carried out, for example, by dissolving either the fluorinated 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 100°C, and more preferably -10 to 80°C. The polymerization time is preferably 0.1 to 50 hours, and more preferably 1 to 24 hours.

[0070] The average degree of polymerization of the repeating units shown in equation (1) can be adjusted by changing the molar ratio of fluorinated compound (3) to compound (4), polymerization temperature, polymerization time, polymerization solution concentration, etc.

[0071] The above manufacturing method typically yields a solution of a fluorine-containing polyamide compound. The obtained solution of the fluorine-containing polyamide compound may be used as is for various applications. Alternatively, the obtained solution of the fluorine-containing polyamide compound may be separated from the fluorine-containing 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 fluorine-containing polyamide compound.

[0072] Next, we will explain how to produce the fluorinated compound (3) shown in formula (3). The fluorinated compound (3) is produced by reacting compound (5) shown in formula (5) with compound (6) shown in formula (6) to obtain compound (7) shown in formula (7), and then oxidizing the obtained compound (7) to produce R 1 A fluorinated compound (3) in which is OH can be produced.

[0073] Formula (5): [ka] (In equation (5), ring A is the same as in equation (3).)

[0074] Formula (6): I-(CF2) n -I (In equation (6), n is the same as in equation (3).) Formula (7): [ka] (In equation (7), n and ring A are the same as in equation (3).)

[0075] As compound (5), the compound represented by formula (5-1) is preferred, and 4-iodotoluene or 3-iodotoluene is more preferred. Formula (5-1) [ka]

[0076] As compound (7), the compound represented by formula (7-1) is preferred. Formula (7-1): [ka] (In equation (7-1), n ​​is the same as in equation (3).)

[0077] Compound (7) is more preferably the compound represented by formula (7-1a) or formula (7-1b). Formula (7-1a): [ka] (In equation (7-1a), n is the same as in equation (3).)

[0078] Formula (7-1b): [ka] (In equation (7-1b), n is the same as in equation (3).)

[0079] Furthermore, R 1 By reacting a fluorinated compound (3) in which is OH with compound (8) represented by formula (8), the desired R 1 A fluorinated compound (3) having a group represented by (for example, an alkoxy group, an aromatic oxy group) can be produced. Formula (8): R-OH (In formula (8), R is a linear or branched alkyl group which may have substituents, or an aromatic group which may have substituents.)

[0080] Also, R 1 By reacting a fluorinated compound (3) in which is OH with a halogenating agent, R 1 A fluorinated compound (3) in which the halogen atom can be produced.

[0081] Also, R 1 By reacting a fluorinated compound (3) in which is OH with a triazine chloride compound, R 1 A fluorinated compound (3) in which the triazinyloxy group is can be produced.

[0082] The reaction between compound (5) and compound (6) can be carried out in a solvent. The solvent should be substantially non-reactive with compounds (5) and (6), yet have the property of dissolving compounds (5) and (6) well, and should also be a good solvent for the resulting compound (7). 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), sulfolane, tetrahydrofuran (THF), cyclohexanone, and acetone. Among these, dimethyl sulfoxide (DMSO) is preferred. The amount of these solvents used is usually 10 to 1000 mL, preferably 50 to 400 mL, per 0.1 moles of compounds (5) and (6).

[0083] The reaction between compound (5) and compound (6) can be carried out, for example, by dissolving either compound (5) or compound (6) in a solvent, adding the other compound to the resulting solution, and then reacting under an inert atmosphere such as nitrogen while stirring. The reaction temperature is preferably 50 to 150°C, and more preferably 100 to 140°C. The reaction time is preferably 0.5 to 50 hours, and more preferably 1 to 30 hours.

[0084] The reaction between compound (5) and compound (6) may be carried out in the presence of a catalyst such as copper or a copper compound, with the addition of a base such as 2,2'-bipyridyl.

[0085] The oxidation of compound (7) can be carried out using an oxidizing agent such as CrO3 or KMnO4. Furthermore, it is preferable to carry out the oxidation of compound (7) in the presence of an acidic compound such as sulfuric acid or acetic acid.

[0086] R 1Examples of halogenating agents used in the reaction between a fluorinated compound (3) whose hydroxyl group is OH and a halogenating agent include thionyl chloride, phosphorus trichloride, and phosphorus pentachloride. The reaction temperature may be, for example, 20 to 100°C. The reaction between the fluorinated compound (3) and the halogenating agent can also be carried out in a solvent. Examples of solvents include ether-based solvents such as diethyl ether and tetrahydrofuran.

[0087] R 1 The reaction between the fluorinated compound (3), which has an OH group, and the triazine chloride compound can be carried out in a solvent in the presence of N-methylmorpholine (NMM), and this reaction can synthesize a triazine-based active diester. The solvent should not substantially react with the fluorinated compound (3), the triazine chloride compound, and N-methylmorpholine (NMM), but should also have the property of dissolving the fluorinated compound (3), the triazine chloride compound, and N-methylmorpholine (NMM) well, and should be a good solvent for the resulting triazine-based active diester. 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), sulfolane, tetrahydrofuran (THF), and acetone. Among these, N-methyl-2-pyrrolidone (NMP) is preferred. The amount of these solvents used is typically 10 to 1000 mL, preferably 50 to 400 mL, per 0.1 mole of the fluorinated compound (3) or triazine chloride compound.

[0088] R 1 The reaction between a fluorinated compound (3) in which is OH and a triazine chloride compound is, for example, R 1This can be carried out by dissolving either a fluorinated compound (3) in which the hydroxyl group is OH, or a triazine chloride compound in a solvent, adding the other compound to the resulting solution, and then reacting it while stirring under an inert atmosphere such as nitrogen. The reaction temperature is preferably 50 to 150°C, and more preferably 100 to 140°C. The reaction time is preferably 0.5 to 50 hours, and more preferably 1 to 30 hours.

[0089] <Method for producing fluorine-containing polybenzoxazole> The fluorinated polybenzoxazoles 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 the fluorinated 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 polybenzoxazoles of this disclosure may be obtained as some or all of the product. In other words, this disclosure also includes mixtures of fluorinated polyamide compounds and fluorinated polybenzoxazoles.

[0090] Dehydration and cyclization of fluorine-containing polyamide compounds can be carried out by heating the fluorine-containing polyamide compound. The heating temperature for dehydration and cyclization is preferably 110 to 450°C, and more preferably 150 to 400°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.

[0091] The fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles of this disclosure have low dielectric constants and low dielectric loss tangents, making them suitable for use as low dielectric materials.

[0092] The fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles of this disclosure have low dielectric constants and low dielectric loss tangents, making them suitable for use as insulating materials for printed circuit boards.

[0093] The fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles of this disclosure have low dielectric constants and low dielectric loss tangents, making them suitable for use as materials for electronic components and electronic devices such as printed circuit boards, flexible printed circuit boards, TAB tapes, COF tapes, and metal wiring, as well as cover substrates for metal wiring, chip components such as IC chips, and base substrates for liquid crystal displays, organic electroluminescent displays, electronic paper, and solar cells.

[0094] The fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles of this disclosure are particularly suitable for use as materials for electronic components and electronic equipment that utilize high frequencies, especially microwaves in the 3-30 GHz range, due to their low dielectric constant and low dielectric loss tangent at high frequencies. For example, they can be suitably used as materials for insulating boards in high-frequency circuits, insulating materials for connecting components, printed circuit boards, bases and antenna covers for high-frequency vacuum tubes, and insulated wires such as coaxial cables and LAN cables. They can also be suitably used as materials for equipment that utilizes microwaves in the 3-30 GHz range, such as satellite communication equipment and mobile phone base stations.

[0095] Printed circuit boards are not particularly limited, but examples include printed wiring boards for electronic circuits in mobile phones, various computers, and communication devices.

[0096] 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.

[0097] The fluorine-containing polyamide compounds and fluorine-containing polybenzoxazoles of this disclosure have low dielectric constants and low dielectric loss tangents, as well as excellent heat resistance, solvent solubility, electrical insulation, and flexibility, and are easily formed into thin films, making them suitable for use in films, resist materials, and the like. In particular,

[0098] The above-mentioned film can be produced by forming the fluorine-containing polyamide compound or fluorine-containing polybenzoxazole of the present disclosure by known film forming methods such as extrusion molding, calendering, or solution casting. Alternatively, the formation of a fluorine-containing polybenzoxazole by dehydration cyclization of the fluorine-containing polyamide compound and the formation of a film can be carried out simultaneously by casting a solution containing the fluorine-containing polyamide compound of the present disclosure and heating it. Furthermore, the film may be subjected to sandblasting, corona treatment, plasma treatment, etching, or the like.

[0099] 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. [Examples]

[0100] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.

[0101] Each value in the examples was measured by the following method.

[0102] (1) Gel permeation chromatography (GPC): Tosoh Corporation high-speed GPC system HLC-8220GPC, column: Tosoh TSKgel α-M, eluent: N-methyl-2-pyrrolidone (NMP) containing 10 mmol / L lithium bromide, column temperature: 40°C, detector: differential refractometer (RI), calibration curve: standard polystyrene (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, 10-20 GHz, TE mode, TM mode)

[0103] <Synthesis Example 1> 1,6-Bis(p-methylphenyl)perfluorohexane (p-6PFBT)

[0104] [ka]

[0105] In a 100 mL three-necked flask equipped with a stirring bar, condenser, and nitrogen inlet tube, p-iodotoluene (11.55 g, 53 mmol) and DMSO (15 mL) were added and dissolved. Next, 1,6-diiodoperfluorohexane (14.40 g, 26 mmol) and copper powder (14.17 g, 223 mmol) were added, and the temperature was gradually increased to 120 °C, where the reaction was carried out for 24 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was removed by distillation under reduced pressure. The resulting crude product was dissolved in diethyl ether (100 mL) and washed with distilled water. The organic layer was separated and dehydrated overnight with anhydrous sodium sulfate. Distillation of diethyl ether using an evaporator yielded a white product (yield: 11.5 g, yield: 92%). Recrystallization was performed using a mixed solvent of methanol and distilled water. White needle-shaped crystals were obtained with a melting point of 65-66 °C.

[0106] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3045(Ar-H), 2987(CH), 2946(CH), 1615(C=C), 1516(C=C), 1298(CF), 1191(CF), 1147(CF) 1 H-NMR (CDCl3, ppm): 2.41 (s, 6H, CH3), 7.28 (d, 4H, Ar-H), 7.44 (d, 4H, Ar-H) 13 C-NMR (CDCl3, ppm): 21.49, 126.84, 129.30, 142.27 19 F-NMR (CDCl3, ppm): -122.09, -121.45, -110.50 Elemental analysis (C 20 H 14 F 12 Calculated values: Carbon 49.81%, Hydrogen 2.93% Measured values: Carbon 49.62%, Hydrogen 2.97%

[0107] <Synthesis Example 2> 1,4-Bis(p-methylphenyl)perfluorobutane (p-4PFBT)

[0108] [ka]

[0109] In a 100 mL three-necked flask equipped with a stirring bar, condenser, and nitrogen inlet tube, p-iodotoluene (11.77 g, 54 mmol) and DMSO (15 mL) were added and dissolved. Next, 1,4-diiodoperfluorobutane (12.25 g, 27 mmol) and copper powder (14.17 g, 220 mmol) were added, and the temperature was gradually increased to 120 °C, where the reaction was carried out for 24 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was removed by distillation under reduced pressure. The resulting crude product was dissolved in diethyl ether (100 mL) and washed with distilled water. The organic layer was separated and dehydrated overnight with anhydrous sodium sulfate. Distillation of diethyl ether using an evaporator yielded a white product. Recrystallization was performed with a mixed solvent of methanol and distilled water to obtain white needle-shaped crystals. The yield was 1.2 g (11% yield), and the melting point was 146-147 °C.

[0110] The physical properties of the obtained product are shown below. 1 H-NMR (CDCl3, ppm): 2.39 (s, 6H, CH3), 7.26 (d, 4H, Ar-H), 7.45 (d, 4H, Ar-H) 13 C-NMR (CDCl3, ppm): 21.49, 126.85, 129.19, 141.98 19 F-NMR (CDCl3, ppm): -121.45, -110.31

[0111] <Synthesis Example 3> 1,6-Bis(m-methylphenyl)perfluorohexane (m-6PFBT)

[0112] [ka]

[0113] In a 100 mL three-necked flask equipped with a stirring bar, condenser, and nitrogen inlet tube, m-iodotoluene (2.18 g, 10 mmol) and DMSO (4 mL) were added and dissolved. Next, 1,6-diiodoperfluorohexane (2.79 g, 5 mmol) and copper powder (3.43 g, 54 mmol) were added, and the temperature was gradually increased to 120 °C, where the reaction was carried out for 24 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was removed by distillation under reduced pressure. The resulting crude product was dissolved in diethyl ether (100 mL) and washed with distilled water. The organic layer was separated and dehydrated overnight with anhydrous sodium sulfate. The liquid product was obtained by distillation of diethyl ether using an evaporator. A colorless, transparent liquid was obtained by vacuum distillation (150 °C / 0.8 Torr). The yield was 1.3 g (55% yield).

[0114] The physical properties of the obtained product are shown below. 1 H-NMR (CDCl3, ppm): 2.41 (s, 6H, CH3), 7.35~7.38 (m, 8H, Ar-H) 13 C-NMR (CDCl3, ppm): 21.14, 124.10, 127.39, 128.51, 129.32, 132.61, 138.62 19 F-NMR (CDCl3, ppm): -121.76, -121.28, -110.51 Elemental analysis (C 20 H 14 F 12 Calculated values: Carbon 49.81%, Hydrogen 2.93% Measured values: Carbon 49.55%, Hydrogen 2.98%

[0115] <Synthesis Example 4> 1,6-Bis(p-carboxyphenyl)perfluorohexane (p-6PFBBA)

[0116] [ka]

[0117] In a 500 mL three-necked flask equipped with a stirring bar, nitrogen inlet tube, thermometer, and dropping funnel, p-6PFBT (10.61 g, 22 mmol), acetic acid (180 mL), and concentrated sulfuric acid (18 mL) were added and dissolved, and the mixture was cooled to 0°C. A solution of chromium trioxide (17.4 g, 174 mmol) dissolved in acetic anhydride (77 mL) was added dropwise, and after the addition was complete, the mixture was allowed to react at room temperature for 12 hours with stirring. After the reaction was complete, the reaction solution was added to distilled water (1 L) to precipitate the product, and the white powdery product was recovered by suction filtration and dried under reduced pressure at 80°C for 12 hours. The dried product was recrystallized in a mixed solvent of DMF and distilled water, and dried under reduced pressure at 100°C for 12 hours to obtain white powder crystals. The yield was 9.7 g (81% yield).

[0118] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3147~2613(OH), 1699(C=O), 1582(C=C), 1516(C=C),1292(CF),1214(CF),1134(CF) 1 H-NMR (DMSO-d6, ppm): 7.80 (d, 4H, Ar-H), 8.13 (d, 4H, Ar-H), 13.44 (s, 2H, COOH) 13 C-NMR (DMSO-d6, ppm): 127.69, 130.49, 131.67, 135.30, 166.76 19 F-NMR (DMSO-d6, ppm): -121.97, -121.52, -110.42 Elemental analysis (C 20 H 10 F 12 O4): Calculated value: Carbon 44.30%, Hydrogen 1.86% Measured values: Carbon 44.09%, Hydrogen 1.97%

[0119] <Synthesis Example 5> 1,4-Bis(p-carboxyphenyl)perfluorobutane (p-4PFBBA)

[0120] [ka]

[0121] In a 500 mL three-necked flask equipped with a stirring bar, nitrogen inlet tube, thermometer, and dropping funnel, p-4PFBT (1.84 g, 4.8 mmol), acetic acid (55 mL), and concentrated sulfuric acid (5.5 mL) were added and dissolved, and the mixture was cooled to 0°C. A solution of chromium trioxide (5.2 g, 52 mmol) dissolved in acetic anhydride (30 mL) was added dropwise, and after the addition was complete, the mixture was allowed to react at room temperature for 12 hours with stirring. After the reaction was complete, the reaction solution was added to distilled water (500 mL) to precipitate the white product, which was collected by suction filtration and dried under reduced pressure at 80°C for 12 hours. The yield was 1.1 g (52% yield).

[0122] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3300~2500(OH), 1698(C=O), 1579(C=C), 1515(C=C), 1291(CF), 1199(CF), 1133(CF) 1 H-NMR (DMSO-d6, ppm): 7.75 (d, 4H, Ar-H), 8.09 (d, 4H, Ar-H), 13.48 (s, 2H, COOH) 13 C-NMR (DMSO-d6, ppm): 127.63, 130.39, 132.22, 135.05, 166.79 19 F-NMR (DMSO-d6, ppm): -121.01, -109.95

[0123] <Synthesis Example 6> 1,6-Bis(m-carboxyphenyl)perfluorohexane (m-6PFBBA)

[0124] [ka]

[0125] In a 500 mL three-necked flask equipped with a stirring bar, nitrogen inlet tube, thermometer, and dropping funnel, m-6PFBT (1.12 g, 2.3 mmol), acetic acid (50 mL), and concentrated sulfuric acid (5 mL) were added and dissolved, then cooled to 0°C. A solution of chromium trioxide (5.4 g, 54 mmol) dissolved in acetic anhydride (30 mL) was added dropwise, and after the addition was complete, the reaction was allowed to proceed at room temperature for 12 hours with stirring. After the reaction was complete, the reaction solution was added to distilled water (500 mL) to precipitate the product, and the white powdery product was collected by suction filtration and dried under reduced pressure at 80°C for 12 hours. The yield was 1.0 g (83% yield), and the melting point was 269-270°C.

[0126] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3400~2600(OH), 1700(C=O), 1614(C=C),1290(CF),1194(CF),1135(CF) 1 H-NMR (DMSO-d6, ppm): 7.74~7.77 (m, 2H, Ar-H), 7.93 (d, 2H, Ar-H), 8.08 (s, 2H, Ar-H), 8.22 (d, 2H, Ar-H), 13.55 (s, 2H, COOH) 13 C-NMR (DMSO-d6, ppm): 127.48, 128.43, 130.63, 131.51, 132.38, 133.98, 166.54 19 F-NMR (DMSO-d6, ppm): -121.47, -121.00, -109.70 Elemental analysis (C 20 H 10 F 12 O4): Calculated value: Carbon 44.30%, Hydrogen 1.86% Actual measured values: Carbon 43.95%, Hydrogen 2.08%

[0127] <Synthesis Example 7> 1,6-Bis(p-chlorocarbonylphenyl)perfluorohexane (p-6PFBBC)

[0128] [ka]

[0129] In a round-bottom flask (100 mL) fitted with a stirring bar, condenser, and calcium chloride tube, p-6PFBBA (5.38 g, 9.9 mmol) and thionyl chloride (40 mL) were added. The mixture was then slowly heated to 85°C and stirred for 1 hour. After cooling to room temperature, excess thionyl chloride was removed under reduced pressure to obtain a solid product. This was purified by sublimation (140°C / 0.8 Torr) to obtain white needle-shaped crystals (yield: 4.4 g, yield: 77%). The melting point was 129-130°C.

[0130] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3064(Ar-H), 1746(C=O), 1146(CF) 1 H-NMR (CDCl3, ppm): 7.75(d,4H,Ar-H), 8.24(d,4H,Ar-H) 13 C-NMR (CDCl3, ppm): 127.78, 131.40, 135.49,136.44, 167.76 19 F-NMR (CDCl3, ppm): -121.60, -121.10, -111.33 Elemental analysis (C 20 H8Cl2F 12 O2): Calculated value: Carbon 41.48%, Hydrogen 1.39% Actual values: Carbon 41.43%, Hydrogen 1.48%

[0131] <Synthesis Example 8> 1,4-Bis(p-chlorocarbonylphenyl)perfluorobutane (p-4PFBBC)

[0132] [ka]

[0133] Similar to Synthesis Example 7, a solid product was obtained by the reaction of p-4PFBBA with thionyl chloride. This was purified by sublimation to obtain a white, needle-shaped crystalline product. The melting point was 109-110°C.

[0134] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3063(Ar-H), 1746(C=O), 1142(CF) 1 H-NMR (CDCl3, ppm): 7.70(d,4H,Ar-H), 8.20(d,4H,Ar-H) 19 F-NMR (CDCl3, ppm): -121.31, -110.35

[0135] <Synthesis Example 9> Bis(4,6-dimethoxy-1,3,5-triazine-2-yl)-p-dodecafluorohexylenedibenzoate (p-DFBBT)

[0136] [ka]

[0137] In a 500 mL three-necked flask equipped with a stirring bar, nitrogen inlet tube, and thermometer, p-6PFBBA (27.11 g, 50 mmol), chlorodimethoxytriazine (CDMT) (17.51 ​​g, 100 mmol), and NMP (400 mL) were added and dissolved, then cooled to 0°C. Afterward, N-methylmorpholine (NMM) (11.59 mL, 105 mmol) was added, and the reaction was carried out at 0°C for 1 hour. After the reaction was complete, the reaction solution was added to 400 mL of an aqueous solution adjusted to pH 3 with acetic acid, and the product was precipitated. This was collected by suction filtration and dried under reduced pressure at 50°C for 12 hours. The crude yield was 32.8 g (crude yield 80%). The dried crude product was recrystallized using a chloroform / hexane mixed solvent and dried under reduced pressure at 50°C for 12 hours to obtain a white powdery product (yield: 21.33 g, yield: 52%).

[0138] The physical properties of the obtained product are shown below. 1 H-NMR (CDCl3, ppm): 4.09 (s, 12H, CH3), 7.76 (d, 4H, Ar-H), 8.30 (d, 4H, Ar-H) 13 C-NMR (CDCl3, ppm): 56.20, 127.64, 130.90, 131.61, 137.01, 137.10, 139.19, 161.54, 170.70, 171.13, 174.39 19 F-NMR (CDCl3, ppm): -123.10, -122.53, -112.65

[0139] <Synthesis Example 10> 1,4-Bis(p-methylphenyl)perfluorobutane (p-4PFBT)

[0140] [ka]

[0141] In a 100 mL three-necked flask equipped with a stirring bar, condenser, and nitrogen inlet tube, p-iodotoluene (20.46 g, 94 mmol) and DMSO (65 mL) were added and dissolved. Next, 1,4-diiodoperfluorobutane (21.27 g, 47 mmol), 2,2-bipyridyl (3.01 g, 19 mmol), and copper powder (21.37 g, 336 mmol) were added, and the temperature was gradually increased to 70°C, where the reaction was carried out for 48 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was removed by distillation under reduced pressure. The resulting crude product was dissolved in diethyl ether (100 mL) and washed with distilled water. The organic layer was separated and dehydrated overnight with anhydrous sodium sulfate. Distillation of the diethyl ether using an evaporator yielded a pale green product. Recrystallization was performed in a mixed solvent of ethyl acetate and hexane to obtain white needle-shaped crystals. The yield was 8.8g (48% yield), and the melting point was 146-147°C.

[0142] The physical properties of the obtained product are shown below. FT-IR (KBr, cm)-1 ):3046(Ar-H), 2987(CH), 2946(CH), 1615(C=C), 1516(C=C), 1298(CF), 1191(CF), 1147(CF) 1 H-NMR (CDCl3, ppm): 2.39 (s, 6H, CH3), 7.27 (d, 4H, Ar-H), 7.44 (d, 4H, Ar-H) 13 C-NMR (CDCl3, ppm): 21.49, 126.85, 129.19, 141.98 19 F-NMR (CDCl3, ppm): -121.45, -110.31 Elemental analysis (C 18 H 14 F8): Calculated values: Carbon 56.55%, Hydrogen 3.69% Actual measured values: Carbon 56.21%, Hydrogen 3.72%

[0143] <Synthesis Example 11> 1,6-Bis(m-chlorocarbonylphenyl)perfluorohexane (m-6PFBBC)

[0144] [ka]

[0145] Similar to Synthesis Example 7, a solid product was obtained by the reaction of m-6PFBBA (7.4 g, 14 mmol) with thionyl chloride (40 mL). This was purified by vacuum distillation to obtain white crystals. The yield was 5.8 g (yield: 72%), and the melting point was 38-39°C.

[0146] The physical properties of the obtained product are shown below. FT-IR (KBr, cm) -1 ):3063(Ar-H), 1746(C=O), 1142(CF) Elemental analysis (C 20 H8Cl2F 12 O2): Calculated value: Carbon 41.48%, Hydrogen 1.39% Actual values: Carbon 41.31%, Hydrogen 1.49%

[0147] <Synthesis Example 12> 1,6-bis(p-carboxyphenyl)perfluorohexane (p-6PFBBA)

[0148]

Chem.

[0149] Ethyl p-iodobenzoate (2.01 g, 7.3 mmol) and DMSO (20 mL) were added to a 100 mL three-necked flask equipped with a stir bar, a condenser tube, and a nitrogen inlet tube and dissolved. Next, 1,6-diiodoperfluorohexane (2.01 g, 3.6 mmol), 2,2'-bipyridyl (0.24 g, 1.5 mmol), and copper powder (2.30 g, 36 mmol) were added, and the temperature was gradually raised to 120 °C and reacted at 120 °C for 24 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and the reaction solution was poured into distilled water (600 mL) to precipitate the product and copper powder. The precipitate was collected by suction filtration and dried under reduced pressure at 60 °C for 12 hours. Toluene (100 mL) was added to the dried precipitate, and the mixture was heated to reflux, and the copper powder was removed by hot filtration. p-6FDEt was obtained by distilling off toluene from the filtrate. This was recrystallized from toluene to obtain white plate-like crystals. The yield was 1.36 g (yield 63%), and the melting point was 100 - 101 °C.

[0150] The physical properties of the obtained p-6FDEt are shown below. 1 H-NMR (CDCl3, ppm): 1.40 - 1.43 (t, 6H, CH3), 4.40 - 4.44 (q, 4H, CH2), 7.66 - 7.68 (d, 4H, Ar-H), 8.16 - 8.17 (d, 4H, Ar-H) 13 C-NMR (CDCl3, ppm): 14.4, 61.7, 127.1, 129.8, 165.6 19 F-NMR (CDCl3, ppm): -121.8, -121.1, -111.0

[0151] 1.30 g, 2.2 mmol of p-6FDEt was mixed with 7 g of 50 wt% potassium hydroxide aqueous solution and methanol (20 mL), and the mixture was heated under reflux for 12 hours. After cooling to room temperature, the mixture was diluted with distilled water, and insoluble matter was filtered off. Concentrated hydrochloric acid was then added to the filtrate to make it acidic. The precipitated p-6PFBBA was collected by suction filtration, washed with distilled water, and recrystallized in a mixed solvent of DMF and distilled water to obtain white powder crystals. The yield was 0.95 g (80% yield).

[0152] <Synthesis Example 13> 1,6-Bis(p-carboxyphenyl)perfluorohexane (p-6PFBBA)

[0153] [ka]

[0154] In a 100 mL three-necked flask equipped with a stirring bar, condenser, and nitrogen inlet tube, p-iodobenzonitrile (1.82 g, 7.9 mmol) and DMSO (20 mL) were added and dissolved. Next, 1,6-diiodoperfluorohexane (2.20 g, 4.0 mmol), 2,2'-bipyridyl (0.25 g, 1.6 mmol), and copper powder (2.52 g, 40 mmol) were added, and the temperature was gradually increased to 120 °C, where the reaction was carried out for 24 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, and the reaction solution was added to distilled water (600 mL) to precipitate the product and copper powder. The precipitate was collected by suction filtration and dried under reduced pressure at 60 °C for 12 hours. Toluene (100 mL) was added to the dried precipitate, and the mixture was heated under reflux. The copper powder was removed by hot filtration, and toluene was removed from the filtrate to obtain p-6FDCN. This was recrystallized with toluene to obtain white crystals. The yield was 0.78g (39% yield), and the melting point was 154-155°C.

[0155] The properties of the obtained p-6FDCN are shown below. 1 H-NMR (CDCl3, ppm): 7.72-7.74 (d, 4H, Ar-H), 7.82-7.83 (d, 4H, Ar-H)

[0156] 0.70 g of p-6FDCN (1.4 mmol) was mixed with 4 g of 50 wt% potassium hydroxide aqueous solution and 10 mL of methanol, and the mixture was heated under reflux for 12 hours. After cooling to room temperature, the mixture was diluted with distilled water, and insoluble matter was filtered off. Concentrated hydrochloric acid was then added to the filtrate to make it acidic. The precipitated p-6PFBBA was collected by suction filtration, washed with distilled water, and recrystallized in a mixed solvent of DMF and distilled water to obtain white powder crystals. The yield was 0.68 g (89% yield).

[0157] <Example 1> Fluorinated polyamide compounds (p-6PFBBC / 6FAP) and fluorinated polybenzoxazoles (p-6PFBBC / 6FAP)

[0158] [ka]

[0159] A three-necked flask (100 mL) fitted with a nitrogen inlet tube was placed in a flask with a stirring bar, heated with a heat gun, and dried. Then, 6FAP (0.70 g, 1.9 mmol) and distilled purified NMP (5 mL) were added and stirred until dissolved. Subsequently, the silylation agent BSA (0.77 g, 3.8 mmol) was added and the mixture was reacted at room temperature for 1 hour. The reaction solution was solidified with liquid nitrogen, and p-6PFBBC (1.10 g, 1.9 mmol) was added and the mixture was stirred at room temperature for 8 hours. The polymerization solution was added to distilled water (400 mL) and the fluorinated polyamide compound (p-6PFBBC / 6FAP) was precipitated. The precipitated polyamide was recovered by suction filtration and dried under reduced pressure at 80°C for 12 hours. The yield was 1.24 g (75% yield). A 20 wt% solution was prepared by dissolving polyamide in distilled and purified NMP. This solution was cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours, and then heat-treated under reduced pressure at 60°C for 3 hours, 100°C for 3 hours, 150°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, and 300°C for 1 hour to obtain a brown transparent cast film (thickness 30 μm).

[0160] The properties of polyamide are as follows: FT-IR (KBr, cm -1 ): 3414 (N-H), 1667 (C=O), 1134 (C-F) Logarithmic viscosity (η inh ): 0.73 dL / g (NMP solution at a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (Mn): 71,000 Weight average molecular weight (Mw): 135,000 Molecular weight distribution (Mw / Mn): 1.9 Solubility (10 wt%): Soluble in NMP, DMAc, THF, TMU

[0161] The properties of polybenzoxazole are as follows. FT-IR (KBr, cm -1 ): 1560 (C=N), 1140 (C-F) Elemental analysis (C 35 H 14 F 18 N2O2): Calculated value: Carbon 50.26%, Hydrogen 1.69%, Nitrogen 3.35% Measured value: Carbon 50.12%, Hydrogen 1.87%, Nitrogen 3.42% Solubility: Insoluble in organic solvents 5% weight loss temperature: 497 °C (in air), 520 °C (in nitrogen) (TGA) 10% weight loss temperature: 518 °C (in air), 539 °C (in nitrogen) (TGA) Carbonization yield: 56% (in nitrogen, 800 °C) (TGA) Glass transition temperature: 210 °C (DSC), 213 °C (TMA), 210 °C (DMA) Coefficient of thermal expansion: 97 ppm / °C (50 - 100 °C) Tensile strength: 48 MPa Elongation at break: 8% Tensile modulus: 1.9 GPa Cut-off wavelength: 335 nm Transmittance at 500 nm: 73% Average refractive index (n ave ): 1.540 (d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) calculated from the refractive index: 2.37 (ε = nave 2 ) Dielectric constant (D k ): 2.34 (10 GHz, TE mode), 2.33 (10 GHz, TM mode), 2.33 (20 GHz, TE mode) Dielectric loss tangent (D f ): 0.0014 (10 GHz, TE mode), 0.0016 (10 GHz, TM mode), 0.0018 (20 GHz, TE mode)

[0162] <Example 2> Fluorinated polyamide compound (p-4PFBBC / 6FAP) and fluorinated polybenzoxazole (p-4PFBBC / 6FAP)

[0163]

Chemical formula

[0164] A stir bar was placed in a three-necked flask (100 mL) equipped with a nitrogen inlet tube. After heating and drying with a heat gun, 6FAP (0.70 g, 1.9 mmol) and distilled NMP (5 mL) were added and stirred until dissolved. Then, silylating agent BSA (0.77 g, 3.8 mmol) was added and reacted at room temperature for 1 hour. The reaction solution was solidified with liquid nitrogen, and p-4PFBBC (0.91 g, 1.9 mmol) was added and stirred at room temperature for 8 hours to react. The polymerization solution was poured into distilled water (400 mL) to precipitate the fluorinated polyamide compound (p-4PFBBC / 6FAP). The precipitated polyamide was collected by suction filtration and dried under reduced pressure at 80 °C for 12 hours. The polyamide was dissolved in distilled NMP to prepare a 20 wt% solution, which was cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours, and then heat-treated under reduced pressure at 60 °C for 3 hours, 100 °C for 3 hours, 150 °C for 1 hour, 200 °C for 1 hour, 250 °C for 1 hour, and 300 °C for 1 hour to obtain a brown transparent cast film (thickness 26 μm).

[0165] The properties of the polyamide are as follows. FT-IR (KBr, cm-1 ):3414(NH), 1667(C=O),1134(CF) Logarithmic viscosity (η inh ): 0.34 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Solubility (10wt%): Soluble in NMP, DMAc, THF, TMU

[0166] The properties of polybenzoxazole are as follows: FT-IR (KBr, cm) -1 ): 1560 (C=N), 1140 (CF) Elemental analysis (C 33 H 14 F 14 N2O2) Calculated values: Carbon 53.82%, Hydrogen 1.92%, Nitrogen 3.80% Actual values: Carbon 53.81%, Hydrogen 2.12%, Nitrogen 4.00% Solubility: Insoluble in organic solvents Temperature at which weight loss of 5% occurs: 467°C (in air), 513°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 500°C (in air), 533°C (in nitrogen) (TGA) Carbonization yield: 53% (in nitrogen, 800°C) (TGA) Glass transition temperature: 226°C (TMA), 228°C (DMA) Thermal expansion coefficient: 83 ppm / °C (80~120°C) Cutoff wavelength: 335nm Transmittance at 500nm: 80% Average refractive index (n ave ):1.560(d line) Birefringence (Δn): 0.002 (d line) Permittivity (ε) obtained from refractive index: 2.43 (ε=n ave 2 ) Dielectric constant (D k ): 2.56 (10GHz, TE mode), 2.46 (10GHz, TM mode), 2.61 (20GHz, TE mode) Dielectric loss tangent (D f): 0.0021 (10GHz, TE mode), 0.0021 (10GHz, TM mode), 0.0018 (20GHz, TE mode)

[0167] <Example 3> Fluorinated polyamide compounds (p-6PFBBC / HAB) and fluorinated polybenzoxazoles (p-6PFBBC / HAB)

[0168] [ka]

[0169] A stirring bar was placed in a three-necked flask (100 mL) fitted with a nitrogen inlet tube, heated with a heat gun to dry it, and then HAB (0.41 g, 1.9 mmol) and distilled NMP (5 mL) were added and stirred to dissolve. Subsequently, the silylation agent BSA (0.77 g, 3.8 mmol) was added and the mixture was reacted at room temperature for 1 hour. The reaction solution was solidified with liquid nitrogen, p-6PFBBC (1.10 g, 1.9 mmol) was added, and the mixture was stirred at room temperature for 8 hours to obtain a solution of the fluorinated polyamide compound (p-6PFBBC / 6FAP). This polymerization solution was cast onto a glass plate and subjected to heat treatment under reduced pressure at room temperature for 3 hours, at 60°C for 3 hours, at 100°C for 3 hours, at 150°C for 1 hour, at 200°C for 1 hour, at 250°C for 1 hour, at 300°C for 1 hour, and at 400°C for 30 minutes to obtain a brown cast film (thickness 24 μm) of fluorinated polybenzoxazole (p-6PFBBC / HAB).

[0170] The properties of polyamide are as follows: FT-IR (KBr, cm) -1 ):3413(NH), 1662(C=O),1139(CF)

[0171] The properties of polybenzoxazole are as follows: FT-IR (KBr, cm) -1 ): 1599 (C=N), 1139 (CF) Elemental analysis (C 32 H 14 F 12N2O2) Calculated values: Carbon 55.99%, Hydrogen 2.06%, Nitrogen 4.08% Actual values: Carbon 56.57%, Hydrogen 2.28%, Nitrogen 4.11% Solubility: Insoluble in organic solvents Temperature at which weight loss of 5% occurs: 486°C (in air), 534°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 515°C (in air), 559°C (in nitrogen) (TGA) Carbonization yield: 54% (in nitrogen, 800°C) (TGA) Glass transition temperature: 246°C (DMA) Thermal expansion coefficient: 66 ppm / °C (60~120°C) Dielectric constant (D k ): 2.60 (10GHz, TE mode), 2.67 (10GHz, TM mode), 2.61 (20GHz, TE mode) Dielectric loss tangent (D f ): 0.0013 (10GHz, TE mode), 0.0013 (10GHz, TM mode), 0.0014 (20GHz, TE mode)

[0172] <Example 4> Fluorinated polyamide compounds (p-6PFBBC / APP) and fluorinated polybenzoxazoles (p-6PFBBC / APP)

[0173] [ka]

[0174] Using APP instead of 6FAP as in Example 1, a polyamide was synthesized in the same manner, and a polybenzoxazole film (brown transparent, 35 μm thick) was prepared by heat treatment at 300°C for 1 hour.

[0175] The properties of polyamide are as follows: FT-IR (KBr, cm) -1 ):3414(NH), 1655(C=O),1134(CF) Logarithmic viscosity (η inh): 0.45 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Number average molecular weight (Mn): 48,000 Weight average molecular weight (Mw): 96,000 Molecular weight distribution (Mw / Mn): 2.0 Solubility (10wt%): Soluble in NMP, DMAc, THF, TMU

[0176] The properties of polybenzoxazole are as follows: FT-IR (KBr, cm) -1 ): 1559 (C=N), 1140 (CF) Solubility: Insoluble in organic solvents Temperature at which weight loss of 5% occurs: 439°C (in air), 493°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 457°C (in air), 510°C (in nitrogen) (TGA) Carbonization yield: 55% (in nitrogen, 800°C) (TGA) Glass transition temperature: 175°C (TMA), 171°C (DMA) Thermal expansion coefficient: 95 ppm / °C (60~160°C) Cutoff wavelength: 351nm Transmittance at 500nm: 72% Average refractive index (n ave ):1.580(d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) obtained from refractive index: 2.50 (ε=n ave 2 ) Dielectric constant (D k ): 2.54 (10GHz, TE mode), 2.52 (10GHz, TM mode), 2.51 (20GHz, TE mode) Dielectric loss tangent (D f ): 0.0022 (10GHz, TE mode), 0.0022 (10GHz, TM mode), 0.0021 (20GHz, TE mode)

[0177] <Example 5> Fluorinated polyamide compounds (m-6PFBBC / HAB) and fluorinated polybenzoxazoles (m-6PFBBC / HAB)

[0178] [ka]

[0179] Using m-6PFBBC instead of p-6PFBBC as in Example 3, a polyamide was synthesized in the same manner, and a polybenzoxazole film (brown transparent, 40 μm thick) was prepared by heat treatment at 350°C for 1 hour.

[0180] The properties of polyamide are as follows: FT-IR (KBr, cm) -1 ):3414(NH), 1660(C=O),1134(CF) Logarithmic viscosity (η inh ): 0.47 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Solubility (10wt%): Soluble in NMP, DMAc, TMU

[0181] The properties of polybenzoxazole are as follows: FT-IR (KBr, cm) -1 ): 1559 (C=N), 1140 (CF) Solubility: Insoluble in organic solvents Temperature at which weight loss of 5% occurs: 476°C (in air), 512°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 509°C (in air), 541°C (in nitrogen) (TGA) Carbonization yield: 59% (in nitrogen, 800°C) (TGA) Glass transition temperature: 227°C (TMA), 225°C (DMA) Thermal expansion coefficient: 68 ppm / °C (100~200°C) Average refractive index (n ave ):1.645(d line) Birefringence (Δn): 0.004 (d line) Permittivity (ε) obtained from refractive index: 2.70 (ε=n ave2 ) Dielectric constant (D k ): 2.63 (10GHz, TE mode), 2.63 (10GHz, TM mode), 2.64 (20GHz, TE mode) Dielectric loss tangent (D f ): 0.0027 (10GHz, TE mode), 0.0029 (10GHz, TM mode), 0.0026 (20GHz, TE mode)

[0182] <Example 6> Fluorinated polyamide compounds (p-6PFBBC / m-6PFBBC / 6FAP) and fluorinated polybenzoxazoles (p-6PFBBC / m-6PFBBC / 6FAP)

[0183] [ka]

[0184] Using p-6PFBBC (50 mol%) and m-6PFBBC (50 mol%) instead of p-6PFBBC as in Example 1, polyamides were synthesized in the same manner, and a polybenzoxazole film (brown transparent, 28 μm thick) was prepared by heat treatment at 300°C for 1 hour.

[0185] The properties of polyamide are as follows: Logarithmic viscosity (η inh ): 0.32 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C)

[0186] The properties of polybenzoxazole are as follows: Temperature at which weight loss of 5% occurs: 463°C (in air), 499°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 489°C (in air), 523°C (in nitrogen) (TGA) Carbonization yield: 50% (in nitrogen, 800°C) (TGA) Glass transition temperature: 192°C (TMA), 191°C (DMA) Thermal expansion coefficient: 84 ppm / °C (80~160°C) Average refractive index (nave ):1.541(d line) Birefringence (Δn): 0.002 (d line) Permittivity (ε) calculated from refractive index: 2.38 (ε=n ave 2 ) Dielectric constant (D k ): 2.35 (10GHz, TE mode), 2.37 (10GHz, TM mode), 2.37 (20GHz, TE mode) Dielectric loss tangent (D f ): 0.0020 (10GHz, TE mode), 0.0021 (10GHz, TM mode), 0.0021 (20GHz, TE mode)

[0187] <Comparative Example 1> Fluorinated polyamide compounds (p-6FDC / 6FAP) and fluorinated polybenzoxazoles (p-6FDC / 6FAP)

[0188] [ka]

[0189] Using p-6FDC instead of p-6PFBBC as in Example 1, a polyamide was synthesized in the same manner, and a polybenzoxazole film (pale yellow transparent, 58 μm thick) was prepared by heat treatment at 350°C for 1 hour.

[0190] The properties of polyamide are as follows: Logarithmic viscosity (η inh ): 0.58 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Number average molecular weight (Mn): 51,000 Weight average molecular weight (Mw): 97,000 Molecular weight distribution (Mw / Mn): 1.9

[0191] The properties of polybenzoxazole are as follows: Temperature at which weight loss of 5% occurs: 489°C (in air), 512°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 512°C (in air), 531°C (in nitrogen) (TGA) Carbonization yield: 55% (in nitrogen, 800°C) (TGA) Glass transition temperature: 299°C (TMA), 309°C (DMA) Thermal expansion coefficient: 62 ppm / °C (60~200°C) Average refractive index (n ave ):1.560(d line) Birefringence (Δn): 0.000 (d line) Permittivity (ε) obtained from refractive index: 2.43 (ε=n ave 2 ) Dielectric constant (D k ): 2.44 (10GHz, TE mode), 2.44 (10GHz, TM mode), 2.39 (20GHz, TE mode) Dielectric loss tangent (D f ): 0.0046 (10GHz, TE mode), 0.0053 (10GHz, TM mode), 0.0045 (20GHz, TE mode)

[0192] <Comparative Example 2> Fluorinated polyamide compounds (p-6FDC / APP) and fluorinated polybenzoxazoles (p-6FDC / APP)

[0193] [ka]

[0194] Using p-6FDC instead of p-6PFBBC as in Example 4, a polyamide was synthesized in the same manner, and a polybenzoxazole film (brown transparent, 40 μm thick) was prepared by heat treatment at 350°C for 1 hour.

[0195] The properties of polyamide are as follows: Logarithmic viscosity (η inh ): 0.53 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30°C) Number average molecular weight (Mn): 50,000 Weight average molecular weight (Mw): 115,000 Molecular weight distribution (Mw / Mn): 2.3

[0196] The properties of polybenzoxazole are as follows: Temperature at which weight loss of 5% occurs: 435°C (in air), 514°C (in nitrogen) (TGA) Temperature at which weight loss of 10% occurs: 476°C (in air), 527°C (in nitrogen) (TGA) Carbonization yield: 64% (in nitrogen, 800°C) (TGA) Glass transition temperature: 283°C (TMA), 278°C (DMA) Thermal expansion coefficient: 69 ppm / °C (80~200°C) Average refractive index (n ave ):1.613(d line) Birefringence (Δn): 0.002 (d line) Permittivity (ε) obtained from refractive index: 2.60 (ε=n ave 2 ) Dielectric constant (D k ): 2.50 (10GHz, TE mode), 2.51 (10GHz, TM mode), 2.51 (20GHz, TE mode) Dielectric loss tangent (D f ): 0.0036 (10GHz, TE mode), 0.0042 (10GHz, TM mode), 0.0042 (20GHz, TE mode)

Claims

1. Fluorine-containing polyamide compounds having repeating units shown in formula (1) (excluding fluorine-containing polyamide compounds having repeating units shown in the following formula (α-1)). Formula (1): 【Chemistry 44】 (In formula (1), n ​​is an integer from 1 to 8, L is a linear or branched non-fluorinated alkylene group or a linear or branched fluorinated alkylene group, and ring A and ring B independently represent a benzene ring, a naphthalene ring, a biphenyl ring, anthracene ring, or a terphenyl ring.) Formula (α-1): 【Chemistry 48】

2. The fluorine-containing polyamide compound according to claim 1, wherein the repeating unit shown in formula (1) is the repeating unit shown in formula (1-1). Formula (1-1): 【Chemistry 45】 (In equation (1-1), n ​​and L are as described above.)

3. The fluorine-containing polyamide compound according to claim 1 or 2, wherein the average degree of polymerization of the repeating units represented by formula (1) is 2 to 100.

4. Fluorine-containing polybenzoxazoles having repeating units shown in formula (2) (excluding fluorine-containing polybenzoxazoles having repeating units shown in formula (α-2) below). Formula (2): 【Chemistry 46】 (In formula (2), n is an integer from 1 to 8, L is a linear or branched non-fluorinated alkylene group or a linear or branched fluorinated alkylene group, and ring A and ring B independently represent a benzene ring, a naphthalene ring, a biphenyl ring, anthracene ring, or a terphenyl ring.) Formula (α-2): 【Chemistry 49】

5. The fluorine-containing polybenzoxazole according to claim 4, wherein the repeating unit shown in formula (2) is the repeating unit shown in formula (2-1). Formula (2-1): 【Chemistry 47】 (In equation (2-1), n ​​and L are as described above.)

6. The fluorine-containing polybenzoxazole according to claim 4 or 5, wherein the average degree of polymerization of the repeating units shown in formula (2) is 2 to 100.

7. A low-dielectric material containing a fluorine-containing polyamide compound according to claim 1 or 2, or a fluorine-containing polybenzoxazole according to claim 4 or 5.

8. An insulating material for a printed circuit board containing a fluorine-containing polyamide compound according to claim 1 or 2, or a fluorine-containing polybenzoxazole according to claim 4 or 5.

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