WO2023219085A1 - Fluorinated polyamide compound, fluorinated polyimide compound, low dielectric material, and high-frequency electronic component - Google Patents

Abstract

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

Description

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

The present disclosure relates to fluorinated polyamide compounds, fluorinated polyimide compounds, low dielectric materials, and high frequency electronic components.

Patent Document 1 describes a fluorinated nitrogen-containing heterocycle-containing compound having a repeating unit represented by formula (3).

(In formula (3), n is an integer of 4 to 8, Rf is a single bond, -SO ₂ -, -O-, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group , Ring C represents an imide ring or benzimidazole ring which may have a substituent.)

Japanese Patent Application Publication No. 2021-178956

An object of the present disclosure is to provide a soluble fluorinated polyamide compound from which a fluorinated polyimide compound having a low dielectric constant and a low dielectric loss tangent can be obtained. Another object of the present disclosure is to provide a fluorinated polyimide compound that has a low dielectric constant and a low dielectric loss tangent.

According to a first aspect of the present disclosure, a fluorinated polyamide compound having a repeating unit represented by formula (1) is provided.
Formula (1):

(In formula (1), n is an integer of 1 to 8, Ring A and Ring B are independently hydrocarbon rings with or without substituents, R is independently H, linear, branched A chain or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group, or a fluorine group with or without a substituent an aromatic group, L is a linking group, and R ¹ is independently OH, a linear or branched alkoxy group that may have a substituent, or a linear or branched alkoxy group that may have a substituent. Represents an aromatic oxy group or a halogen atom.)

According to the present disclosure, it is possible to provide a soluble fluorinated polyamide compound from which a fluorinated polyimide compound having a low dielectric constant and a low dielectric loss tangent can be obtained. Further, according to the present disclosure, it is possible to provide a fluorinated polyimide compound that has a low dielectric constant and a low dielectric loss tangent.

Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

<Fluorinated polyamide compound>
The fluorinated polyamide compound of the present disclosure has a repeating unit represented by formula (1).
Formula (1):

(In formula (1), n is an integer of 1 to 8, Ring A and Ring B are independently hydrocarbon rings with or without substituents, R is independently H, linear, branched A chain or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group, or a fluorine group with or without a substituent an aromatic group, L is a linking group, and R ¹ is independently OH, a linear or branched alkoxy group that may have a substituent, or a linear or branched alkoxy group that may have a substituent. Represents an aromatic oxy group or a halogen atom.)

The fluorinated polyamide compound of the present disclosure contains a repeating unit represented by formula (1), and ring B is bonded via a linear perfluoroalkylene group (-(CF ₂ ) _n -) Therefore, the fluorinated polyimide compound derived from the fluorinated polyamide compound of formula (1) is a conventional fluorinated polyimide compound in which ring B is bonded via a perfluoroisopropylidene group (-C(CF ₃ ) ₂ -). Compared to conventional fluorinated polyimide compounds derived from fluorinated polyamide compounds, the dielectric constant and dielectric loss tangent are much lower. Furthermore, the fluorinated polyamide compound of the present disclosure has the property of being soluble in organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

n represents an integer from 1 to 8. n is preferably an integer of 4 to 8, more preferably 4 to 6, since the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound can be further lowered. .

Ring A is a hydrocarbon ring with or without a substituent. Ring A is preferably 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, and more preferably a benzene ring.

Ring B is a hydrocarbon ring with or without a substituent. Ring B is preferably 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, and more preferably a benzene ring.

R is independently H, a linear, branched or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group; or a fluorinated aromatic group with or without substituents. As R, H is preferable.

L is a linking group. L is preferably a single bond, -O-, -SO ₂ -, -CO-, a divalent non-fluorinated organic group or a divalent fluorinated organic group, and more preferably a divalent fluorinated organic group.

The above-mentioned non-fluorinated organic group is a divalent organic group that does not have a fluorine atom. The non-fluorinated organic group is preferably a linear or branched non-fluorinated alkylene group or a non-fluorinated arylene group.

The above fluorinated organic group is a divalent organic group having one or more fluorine atoms. The fluorinated organic group is preferably a linear or branched fluorinated alkylene group or a fluorinated arylene group.

L is preferably a linear or branched fluorinated alkylene group, since it can further lower the dielectric constant and dielectric loss tangent of a fluorinated polyimide compound derived from a fluorinated polyamide compound, and perfluoroalkylene More preferably, it is a group. The perfluoroalkylene group preferably has 1 to 8 carbon atoms.

As the fluorinated alkylene group, a perfluoroalkylene group represented by the following formula is more preferable because it can further lower the dielectric constant and dielectric loss tangent of a fluorinated polyimide compound derived from a fluorinated polyamide compound.
Formula: -(CF ₂ ) _n1 -
(In the formula, n1 represents an integer from 1 to 8.)

n1 is preferably an integer of 4 to 8, more preferably 4 to 6, since it is possible to further lower the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound derived from the fluorinated polyamide compound. , more preferably 4 or 6.

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.

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

Examples of substituents that the alkoxy group and aromatic oxy group as ^R1 may have include 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. A group is preferable, and an alkoxy group is more preferable.

Examples of the aromatic oxy group as R ¹ include a phenoxy group that does not have a substituent, a triazinyloxy group that may have a substituent, and the like.

R ¹ is independently OH, an unsubstituted phenoxy group, a methoxy group, an ethoxy group, a chlorine atom, or

is preferred.

The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-1).
Formula (1-1):

(In formula (1-1), n, L and R ¹ are as described above.)

Examples of the fluorinated polyamide compound include compounds represented by the following formulas.

(In the formula, n, L and R ¹ are as described above. R ² independently represents H or a monovalent organic group. The average degree of polymerization of the repeating unit represented by formula (1), (Can have repeating units shown in parentheses.)

R ² is independently H or a monovalent organic group. The monovalent organic group is a monovalent group containing a carbon atom or a group formed by removing one hydrogen atom from an organic compound. The above-mentioned monovalent organic group includes an aliphatic hydrocarbon group that may have a substituent, an aromatic group that may have a substituent, and an aliphatic hydrocarbon group that may have a substituent. Examples include an acyl group and an aromatic acyl group which may have a substituent.

Specific examples of the above-mentioned monovalent organic groups include lower alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ ; -CF ₃ , A fluorine atom-containing lower alkyl group having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms, such as -C ₂ F ₅ , -CH ₂ F, -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ ; phenyl group (having no substituent); benzyl group (having no substituent); phenyl in which 1 to 5 hydrogen atoms are substituted with fluorine atoms such as -C ₆ F ₅ , -CH ₂ C ₆ F ₅ group or benzyl group; -CF 3 of 1 to 5 such as -C ₆ H _5-k (CF _{3 ) k} , -CH ₂ C ₆ H _5-k (CF ₃ ) _k (k is an integer of 1 to 5) phenyl or benzyl groups with hydrogen atoms substituted; aliphatic acyl groups such as acetyl and pivaloyl; aromatic acyl groups such as benzoyl and methylbenzoyl; fluorine such as fluoroacetyl and trifluoroacetyl groups acetyl group; examples include fluorobenzoyl group and trifluoromethylbenzoyl group.

^R2 is independently preferably H or an aromatic group which may have a substituent, more preferably H or a phenyl group which may have a substituent, and H or a phenyl group which may have a substituent. A phenyl group substituted with a phenyl group or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms is more preferred.

In the fluorinated polyamide compound of the present disclosure, the average degree of polymerization of the repeating unit represented by formula (1) is preferably 500 or less, more preferably 300 or less, still more preferably 200 or less, and 2 or more. The number may be 3 or more. The average degree of polymerization is calculated from the number average molecular weight of the fluorinated polyamide compound of the present disclosure.

The number average molecular weight (Mn) of the fluorinated polyamide compound of the present disclosure is preferably 2,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, as measured by gel permeation chromatography in terms of standard polystyrene. , more preferably 500,000 or less.

The molecular weight distribution (Mw/Mn) of the fluorinated polyamide compound of the present disclosure is preferably 1.5 or more, more preferably 2 or more, and preferably 5 or less in terms of standard polystyrene by gel permeation chromatography. , more preferably 4 or less.

The logarithmic viscosity η _inh of the fluorinated polyamide compound of the present disclosure is preferably 0.3 dL/g or more, more preferably 0.5 dL/g or more. The logarithmic viscosity η _inh is determined by dissolving the fluorinated polyamide compound in N-methyl-2-pyrrolidone (NMP) as a solvent to prepare a solution with a solution concentration of 0.5 g/dL, and The viscosity (solution viscosity) at °C can be measured and calculated using the following formula.
Logarithmic viscosity η _inh = ln (solution viscosity/solvent viscosity)/solution concentration

The fluorinated polyamide compound of the present disclosure can be suitably used as a precursor of a fluorinated polyimide compound having a repeating unit represented by formula (2) described below.

<Fluorinated polyimide compound>
The fluorinated polyimide compound of the present disclosure has a repeating unit represented by formula (2).
Formula (2):

(In formula (2), n, ring A, ring B, R and L are the same as in formula (1).)

The fluorinated polyimide compound of the present disclosure contains a repeating unit represented by formula (2), and ring B is bonded via a linear perfluoroalkylene group (-(CF ₂ ) _n -) Therefore, compared to conventional fluorinated polyimide compounds in which ring B is bonded via a perfluoroisopropylidene group (-C(CF ₃ ) ₂ -), the dielectric constant and dielectric loss tangent are much lower. .

In formula (2), n, ring A, ring B, R and L are the same as in formula (1), and by having the same suitable structure as in formula (1), the dielectric constant of the fluorinated polyimide compound can be increased. And the dielectric loss tangent can be further lowered.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-1).
Formula (2-1):

(In formula (2-1), n and L are as described above.)

Examples of the fluorinated polyimide compound include compounds represented by the following formulas.

(In the formula, n, L, R ¹ and R ² are as described above. It is the average degree of polymerization of the repeating unit represented by formula (2), and can have the repeating unit shown in parentheses.)

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

The glass transition temperature of the fluorinated polyimide compound of the present 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 rheology (DMA), or thermomechanical analysis (TMA).

In the fluorinated polyimide compound of the present disclosure, the average degree of polymerization of the repeating unit represented by formula (2) is preferably 300 or less, more preferably 200 or less, may be 2 or more, and may be 3 or more. There may be. The average degree of polymerization is calculated from the number average molecular weight of the fluorinated polyimide compound of the present disclosure.

Since the dielectric constant and dielectric loss tangent of the fluorinated polyimide compound can be further lowered, the fluorinated polyimide compound 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. It may be.

The number average molecular weight (Mn) of the fluorinated polyimide compound of the present disclosure is preferably 2,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, as measured by gel permeation chromatography in terms of standard polystyrene. , more preferably 500,000 or less.

The molecular weight distribution (Mw/Mn) of the fluorinated polyimide compound of the present disclosure is preferably 1.5 or more, more preferably 2 or more, and preferably 5 or less in terms of standard polystyrene by gel permeation chromatography. , more preferably 4 or less.

The logarithmic viscosity η _inh of the fluorinated polyimide compound of the present disclosure is preferably 0.3 dL/g or more, more preferably 0.5 dL/g or more. The logarithmic viscosity η _inh is determined by dissolving the fluorinated polyimide compound in N-methyl-2-pyrrolidone (NMP) as a solvent to prepare a solution with a solution concentration of 0.5 g/dL, and The viscosity (solution viscosity) at °C can be measured and calculated using the following formula.
Logarithmic viscosity η _inh = ln (solution viscosity/solvent viscosity)/solution concentration

<Method for producing fluorinated polyamide compound>
The fluorinated polyamide compound of the present disclosure can be suitably produced by polymerizing the compound (3) represented by formula (3) and the compound (4) represented by formula (4).

Formula (3):

(In formula (3), rings A, L and R ² are as described above.)

Formula (4):

(In formula (4), n, ring B, R and R ¹ are as described above. In formula (4), two adjacent -COR ^1s are an acid anhydride bond (-CO-O-CO -) may form a ring with the two carbon atoms to which the two -COR ^1s are bonded.)

As the compound (3), a compound (3-1) represented by the formula (3-1) is preferable.
Formula (3-1):

(In formula (3-1), L and R ² are as described above.)

As the compound (4), a compound (4-1) represented by the formula (4-1) is preferable.
Formula (4-1):

(In formula (4-1), n and R ¹ are as described above. In formula (4-1), two adjacent -COR ¹ 's are acid anhydride bonds (-CO-O-CO- ) may form a ring with the two carbon atoms to which the two -COR ¹ are bonded.)

The polymerization of compound (3) and compound (4) can be carried out in a solvent. The solvent does not substantially react with compound (3) and compound (4), and has the property of dissolving compound (3) and compound (4) well. It is desirable that the solvent be a good solvent for the fluorinated polyimide compound obtained by polymerizing the fluorinated polyimide compound. Examples of such solvents include, but are not limited to, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), Examples include 1,3-dimethylimidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropylene urea (DMPU), cyclohexanone, cyclopentanone, sulfolane, tetrahydrofuran (THF), and acetone. Among them, N-methyl-2-pyrrolidone (NMP) and 1,3-dimethylimidazolidone (DMI) are preferred. The amount of these solvents used is usually 100 to 1000 mL, preferably 50 to 400 mL per 0.1 mol of compound (3) or compound (4).

Polymerization can also be carried out in the presence of additives. For example, in order to obtain a compound with a large molecular weight, inorganic salts such as lithium chloride and calcium chloride may be added. Among these, lithium chloride is preferred as the additive. The amount of additive added is preferably 10% by mass or less, more preferably 5% by mass or less based on the amount of solvent.

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 with stirring under an inert atmosphere such as nitrogen. This can be done by letting The polymerization temperature is preferably -50 to 150°C, more preferably 0 to 100°C, even more preferably 20 to 80°C. The polymerization time is preferably 0.1 to 50 hours, more preferably 1 to 24 hours.

The average degree of polymerization of the repeating unit represented by formula (1) can be controlled by adjusting the molar ratio of compound (3) and compound (4), polymerization temperature, polymerization time, polymerization solution concentration, etc.

By the above production method, a polymerization solution of a fluorinated polyamide compound is usually obtained. The obtained polymerization solution of the fluorinated polyamide compound may be used as it is for various purposes. In addition, the obtained solution of the fluorinated polyamide compound is poured into a poor solvent such as methanol or water to separate the fluorinated polyamide compound, and then purified by a reprecipitation method to remove byproducts, inorganic salts, etc. By doing so, a highly pure fluorinated polyamide compound may be obtained.

<Method for producing fluorinated polyimide compound>
The fluorinated polyimide compound of the present disclosure can be suitably produced by obtaining a fluorinated polyamide compound by the above production method and then subjecting the fluorinated polyamide compound to cyclodehydration. In addition, when producing a fluorinated polyamide compound, if the polymerization of compound (3) and compound (4) is carried out in a heated state, part or all of the compound is dehydrated and cyclized, resulting in formula (2). A compound having a repeating unit shown may be formed, resulting in a fluorinated polyimide compound of the present disclosure as part or all of the product. That is, the present disclosure also includes mixtures of fluorinated polyamide compounds and fluorinated polyimide compounds.

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

Since the fluorinated polyimide compound of the present disclosure has a low dielectric constant and a low dielectric loss tangent, the fluorinated polyamide compound and the fluorinated polyimide compound can be suitably used as a low dielectric material.

Since the fluorinated polyimide compound of the present disclosure has a low dielectric constant and a low dielectric loss tangent, the fluorinated polyamide compound and the fluorinated polyimide compound can be suitably used as semiconductor package substrates, flexible printed circuit boards, and rigid printed circuit boards.

The fluorinated polyimide compound of the present disclosure has a low dielectric constant and a low dielectric loss tangent. Tapes, COF tapes, metal wiring, etc., cover substrates for metal wiring, chip components such as IC chips, interlayer insulating films, base substrates for liquid crystal displays, organic electroluminescent displays, electronic paper, solar cells, etc. It can be suitably used as a material for electronic parts and devices such as adhesive sheets, prepregs, and primers.

The fluorinated polyimide compound of the present disclosure has a particularly low dielectric constant and a low dielectric loss tangent at high frequencies. It can be suitably used as a material for electronic parts and electronic devices. For example, it can be suitably used as a material for high-frequency electronics parts, insulating plates for high-frequency circuits, insulating materials for connecting parts, printed circuit boards, bases and antenna covers for high-frequency vacuum tubes, coated wires for coaxial cables, LAN cables, etc. Furthermore, it can be suitably used as a material for equipment such as satellite communication equipment and mobile phone base stations that utilize microwaves of 3 to 30 GHz.

Although the printed circuit board is not particularly limited, examples thereof include printed wiring boards for electronic circuits such as mobile phones, smartphones, various computers, and communication devices.

Coaxial cables are not particularly limited, but examples include those 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.

The fluorinated polyimide compound of the present disclosure has a low dielectric constant and a low dielectric loss tangent, and also has excellent heat resistance, solvent solubility, electrical insulation, colorless transparency, and flexibility, and can be easily formed into a thin film. Therefore, fluorinated polyamide compounds and fluorinated polyimide compounds can be suitably used for interlayer insulating films, films, adhesive sheets, prepregs, primers, polymer electrolyte membranes, resist materials, and the like. Among these, it is suitable for film.

The above film can be produced by molding the fluorinated polyamide compound or fluorinated polyimide compound of the present invention by a known film molding method such as an extrusion molding method, a calendar molding method, a solution casting method, or the like. Further, by casting a solution containing the fluorinated polyamide compound of the present invention and heating it, it is also possible to simultaneously produce a fluorinated polyimide compound by cyclodehydration of the fluorinated polyamide compound and form a film. Furthermore, the film may be subjected to sandblasting treatment, corona treatment, plasma treatment, etching treatment, etc.

Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

<1> According to the first aspect of the present disclosure,
A fluorinated polyamide compound having a repeating unit represented by formula (1) is provided.
Formula (1):

(In formula (1), n is an integer of 1 to 8, Ring A and Ring B are independently hydrocarbon rings with or without substituents, R is independently H, linear, branched A chain or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group, or a fluorine group with or without a substituent an aromatic group, L is a linking group, and R ¹ is independently OH, a linear or branched alkoxy group that may have a substituent, or a linear or branched alkoxy group that may have a substituent. Represents an aromatic oxy group, siloxy group, or halogen atom.)
<2> According to the second aspect of the present disclosure,
A fluorinated polyamide compound according to the first aspect is provided, 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 the present disclosure,
A fluorinated polyamide compound according to the first or second aspect is provided, 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 the present disclosure,
Fluorination according to any one of the first to third aspects, wherein L is a single bond, -O-, -SO ₂ -, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group A polyamide compound is provided.
<5> According to the fifth aspect of the present disclosure,
A fluorinated polyamide compound according to any one of the first to fourth aspects is provided, wherein the repeating unit represented by formula (1) is a repeating unit represented by formula (1-1).
Formula (1-1):

(In formula (1-1), n, L and R ¹ are as described above.)
<6> According to the sixth aspect of the present disclosure,
A fluorinated polyimide compound having a repeating unit represented by formula (2) is provided.
Formula (2):

(In formula (2), n is an integer of 1 to 8, Ring A and Ring B are independently hydrocarbon rings with or without substituents, R is independently H, linear, branched A chain or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group, or a fluorine group with or without a substituent aromatic group, L represents a linking group)
<7> According to the seventh aspect of the present disclosure,
A fluorinated polyimide compound according to a sixth aspect is provided, 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 the present disclosure,
A fluorinated polyimide compound according to the sixth or seventh aspect is provided, 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 the present disclosure,
Fluorination according to any of the sixth to eighth aspects, wherein L is a single bond, -O-, -SO ₂ -, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group A polyimide compound is provided.
<10> According to the tenth aspect of the present disclosure,
There is provided a fluorinated polyimide compound according to any one of the sixth to ninth aspects, wherein the repeating unit represented by formula (2) is a repeating unit represented by formula (2-1).
Formula (2-1):

(In formula (2-1), n and L are as described above.)
<11> According to the eleventh aspect of the present disclosure,
There is provided a fluorinated polyimide compound according to any one of the sixth to tenth aspects, which has a dielectric loss tangent (Df) of 0.005 or less at 10 GHz.
<12> According to the twelfth aspect of the present disclosure,
A low dielectric material containing a fluorinated polyamide compound according to any one of the first to fifth aspects or a fluorinated polyimide compound according to any one of the sixth to eleventh aspects is provided.
<13> According to the thirteenth aspect of the present disclosure,
A high frequency electronics component containing a fluorinated polyamide compound according to any one of the first to fifth aspects or a fluorinated polyimide compound according to any one of the sixth to eleventh aspects is provided.

Next, embodiments of the present disclosure will be described with examples, but the present disclosure is not limited to these examples.

Each numerical value in Examples was measured by the following method.

(1) GPC: Tosoh Corporation high-speed GPC system HLC-8220GPC (column: Tosoh TSKgel (α-M), column temperature: 45°C, detector: UV-8020, wavelength 254 nm, eluent: N-methyl- 2-pyrrolidone (NMP) (contains 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 spectrum (NMR): BRUKER AC400P
(4) Thermogravimetry (TGA): TG/DTA7300 manufactured by Hitachi High-Tech Science Co., Ltd., heating rate 10°C/min
(5) Differential scanning calorimetry (DSC): DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd., heating rate 20°C/min
(6) Thermomechanical analysis (TMA): TMA7000 manufactured by Hitachi High-Tech Science Co., Ltd., heating rate 10°C/min
(7) Dynamic viscoelasticity measurement (DMA): DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd., heating rate 2°C/min
(8) Ultraviolet-visible 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 10 GHz and 20 GHz, cavity resonator TM mode 10 GHz)

<Synthesis example 1>
Synthesis of 4,4'-(1,6-perfluorohexylene)dianiline (6PFDA)

Add 4-iodoacetanilide (18.49 g, 70.8 mmol), 1,6-diiodoperfluorohexane (21.58 g, 38.9 mmol), and dimethyl sulfoxide (DMSO, 90 mL) to an eggplant flask (300 mL) and dissolve. I let it happen. Copper powder (22.51 g, 354 mmol) was added, and the mixture was reacted at 120° C. for 24 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature and the copper powder was removed by suction filtration. THF and brine were added to the filtrate, and the THF layer was collected. After dehydration over anhydrous sodium sulfate, THF was distilled off to obtain a light brown product (6PFDAC). This was recrystallized with a mixed solvent of THF/hexane to obtain white needle-like crystals. The yield was 9.8 g (yield: 50%). The melting point was 212-213°C.
¹ H-NMR (DMSO-d ₆ , ppm): 10.30 (s, 2H, NH), 7.78 (d, 4H, ArH), 7.56 (d, 4H, ArH), 2.08 ( s, 6H, _CH3 ).
^19F -NMR (DMSO-d ₆ , ppm): -108.9, -121.2, -121.7
FT-IR (KBr, cm ^-1 ): 3308 (NH), 1681 (C=O), 1183-1106 (C-F)
6PFDAC (9.77 g, 17.2 mmol) and ethanol (180 mL) were placed in an eggplant flask (500 mL), concentrated hydrochloric acid (31 mL) was added, and 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 hydrogen carbonate. Methylene chloride was added to the reaction solution and the organic layer was collected. Anhydrous sodium sulfate was added to the organic layer for dehydration. Methylene chloride was distilled off to obtain a pale yellow product (6PFDA). This was recrystallized from 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-d ₆ , ppm): 7.21 (s, 4H, ArH), 6.65 (s, 4H, ArH), 5.85 (s, 4H, NH)
^13C -NMR (DMSO-d ₆ , ppm): 152.4, 127.8, 113.1
^19F -NMR (DMSO-d ₆ , 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 N ₂ F ₁₂ ):
Calculated value C, 44.60%; H, 2.50%; N, 5.78%
Actual value C, 44.53%; H, 2.46%; N, 5.65%

<Synthesis example 2>
Synthesis of 4,4'-(1,6-perfluorohexylene)diphthalic anhydride (6PFDAH)

In an eggplant 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. Thereafter, copper powder (13.9 g, 219 mmol) was added, and the mixture was reacted at 120° C. for 24 hours under a nitrogen stream. 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, the organic layer was collected, and after dehydration over anhydrous sodium sulfate, t-butyl methyl ether was distilled off to obtain a white product (6BFBOX). This was recrystallized from methanol to obtain white needle-like crystals. The yield was 8.5 g, 77%, and the melting point was 84-85°C.
¹ H-NMR (CDCl ₃ , ppm): 7.33 (s, 2H, ArH), 7.31 (d, 2H, ArH), 7.23 (d, 2H, ArH), 2.31 (s, 12H, _CH3 )
^13C -NMR (CDCl ₃ , ppm): 140.9, 137.1, 129.8, 127.8, 126.8, 124.4, 19.8
^19F -NMR (CDCl ₃ , ppm): -132.2, -122.7, -111.6
FT-IR (KBr, cm ^-1 ): 2944 (C-H), 2924 (C-H), 1222 (C-F), 1130 (C-F)
Elemental analysis (C ₂₂ H ₁₈ F ₁₂ ): Calculated values C, 51.77%; H, 3.56%
Actual value C, 51.53%; H, 3.58%
6PFBOX (4.0 g, 7.8 mmol), t-butyl alcohol (40 mL), and distilled water (160 mL) were placed in an eggplant flask (500 mL) and stirred. KMnO ₄ (30.4 g, 192 mmol) was added at room temperature, reacted at 85° C. for 1 hour, and reacted at 100° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, and a saturated aqueous solution of sodium hydrogen carbonate (8.1 g, 96 mmol) was added to the reaction solution, followed by stirring for 30 minutes. The reaction solution was filtered through Celite, and concentrated hydrochloric acid was added to the filtrate to precipitate a white product. t-Butyl methyl ether (100 mL) was added and stirred for 1 hour to dissolve the product in the organic layer, which was collected. The organic layer was washed with brine until neutral. The organic layer was dried over anhydrous sodium sulfate, and t-butyl methyl ether was distilled off to obtain a white product (6PFBPA). This was recrystallized from a mixed solvent of distilled water/acetone to obtain white needle-like crystals. The yield was 3.8 g (yield: 77%), and the melting point was 207-208°C.
¹ H-NMR (DMSO-d ₆ , ppm): 13.6 (br, 4H, OH), 7.94-7.93 (m, 4H, ArH), 7.89 (d, 2H, ArH)
^13C -NMR (DMSO-d ₆ , ppm): 168.0, 167.0, 137.6, 132.9, 129.7, 129.4, 129.3, 126.8
^19F -NMR (DMSO-d ₆ , ppm): -111.6, -122.7, -123.2
FT-IR (KBr, cm ^-1 ): 3114 (O-H), 1736 (C=O), 1222 (C-F), 1135 (C-F)
Elemental analysis (C ₂₂ H ₁₀ O ₈ F ₁₂ ): Calculated value C, 41.92%; H, 1.60%
Actual value C, 41.72%; H, 1.78%
6PFBPA (3.5 g, 5.6 mmol) and acetic anhydride (18 mL) were placed in an eggplant flask (100 mL), and the mixture was stirred at 140° C. for 15 hours under a nitrogen stream. After the reaction, acetic anhydride was distilled off under reduced pressure to obtain a pale yellow product. This was recrystallized with a mixed solvent of dehydrated ethyl acetate and dehydrated hexane to obtain light brown needle-shaped crystals, and further purified by sublimation (185°C/0.2 Torr) to obtain white powdery crystals (6PFDAH). Ta. The yield was 1.9 g (yield: 58%), and the melting point was 190-191°C.
¹ H-NMR (CDCl ₃ , ppm): 8.27 (s, 2H, ArH), 8.21 (d, 2H, ArH), 8.15 (d, 2H, ArH)
^13C -NMR (CDCl ₃ , ppm): 161.4, 161.3, 134.8, 134.4, 132.0, 126.4, 124.8
^19F -NMR (CDCl ₃ , ppm): -112.1, -122.3, -122.5
FT-IR (KBr, cm ^-1 ): 3140-3010 (Ar-H), 1862 (C=O), 1798 (C=O), 1134 (C-F)
Elemental analysis _{( C22H6O6F12} ): Calculated value C, _44.46 %; _H , 1.02%
Actual value C, 44.28%; H, 1.16%

<Synthesis example 3>
Synthesis of 4,4'-(1,4-perfluorobutylene)diphthalic anhydride (4PFDAH)

In an eggplant 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 added and dissolved. Thereafter, copper powder (13.7 g, 215 mmol) was added, and the mixture was reacted at 70° C. for 48 hours under a nitrogen stream. After the reaction, the solution 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 collected. The organic layer was dehydrated by adding anhydrous sodium sulfate, and t-butyl methyl ether was distilled off to obtain a crude product. This was recrystallized from a mixed solvent of methanol/distilled water to obtain white needle-like crystals (4PFBOX). The yield was 3.7 g (yield: 42%), and the melting point was 89-90°C.
¹ H-NMR (CDCl ₃ , 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 (C-H), 1177 (C-F), 1121 (C-F)
4PFBOX (3.5 g, 8.5 mmol), t-butyl alcohol (35 mL), and distilled water (175 mL) were placed in an eggplant flask (500 mL) and suspended by stirring. After adding KMnO ₄ (32.3 g, 204 mmol) to this suspension, it 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 precipitate a white product. t-Butyl methyl ether (100 mL) was added and 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 dried over anhydrous sodium sulfate, and t-butyl methyl ether was distilled off to obtain a white product. This was recrystallized from a mixed solvent of distilled water/acetone to obtain white needle-like crystals (4PFBPA). The yield was 3.0 g, the yield was 66%, and the melting point was 204-205°C.
¹ H-NMR (DMSO-d ₆ , 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 (O-H), 1736 (C=O), 1116 (C-F)
4PFBPA (2.9 g, 5.5 mmol) and acetic anhydride (15 mL) were placed in an eggplant flask (100 mL), and the mixture was reacted at 140° C. for 15 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature and acetic anhydride was distilled off under reduced pressure to obtain a light brown product. This was recrystallized with a mixed solvent of dehydrated ethyl acetate/hexane to obtain light brown needle-shaped crystals, and further purified by sublimation (195°C/0.2 Torr) to obtain white powder crystals (4PFDAH). . The yield was 1.6 g, 58%, and the melting point was 199-200°C.
¹ H-NMR (CDCl ₃ , 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 (C-F)

<Example 1>
Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDA-6PFDAH)

6PFDA (0.726 g, 1.50 mmol) and dehydrated NMP (3 mL) were placed in an eggplant flask (100 mL) equipped with a stirring bar, nitrogen inlet tube, and Dimroth condenser, and dissolved. 6PFDAH (0.891 g, 1.50 mmol) was added to this solution and dissolved with stirring at room temperature. Thereafter, by stirring at 60° C. for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.34 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). An NMP solution (20 wt%) of a fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Thereafter, a pale yellow, translucent fluorinated polyimide compound (6PFDA -6PFDAH) film (thickness: 40 μm) was prepared.
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: 5% insoluble in organic solvents such as NMP, DMAc, DMF, DMI, THF, chloroform, etc. Weight loss temperature: 529°C (in air), 538°C (in nitrogen)
10% weight loss temperature: 544℃ (in air), 554℃ (in nitrogen)
Carbonization yield: 46% (in nitrogen, 800°C)
Glass transition temperature: 159°C (DSC measurement)
Melting point: 350°C (DSC measurement)
Cutoff wavelength: 372nm
Transmittance at 500nm: 27%
Average refractive index (n _ave ): 1.538 (d line)
Dielectric constant (ε) determined from refractive index: 2.60 (ε=1.10×n _ave ² )
Dielectric constant (D _k ): 2.56 (TM, 10 GHz), 2.48 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0015 (TM, 10 GHz), 0.0016 (TE, 20 GHz)

<Example 2>
Fluorinated polyamide compound and fluorinated polyimide compound (BisAAF-6PFDAH)

BisAAF (0.501 g, 1.50 mmol) and dehydrated NMP (3 mL) were placed in an eggplant flask (100 mL) equipped with a stirring bar, nitrogen inlet tube, and Dimroth condenser, and dissolved. 6PFDAH (0.891 g, 1.50 mmol) was added to this solution and dissolved with stirring at room temperature. Thereafter, by stirring at 60° C. for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.34 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). An NMP solution (20 wt%) of a fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Thereafter, a pale yellow and transparent fluorinated polyimide compound (BisAAF- 6PFDAH) film (thickness: 29 μm) was prepared.
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: N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidone (DMI), tetrahydrofuran (THF) ), γ-butyrolactone, soluble in chloroform Logarithmic viscosity (η _inh ): 0.38 dL/g (0.5 g/dL concentration NMP solution, measured at 30°C)
Number average molecular weight ( _Mn ): 30,000
Weight average molecular weight ( _Mw ): 87,000
Molecular weight distribution ( _Mw / _Mn ): 3.0
5% weight loss temperature: 513℃ (in air), 526℃ (in nitrogen)
10% weight loss temperature: 533℃ (in air), 545℃ (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): 81ppm/℃ (temperature range from 100℃ to 150℃, TMA measurement)
Cutoff wavelength: 341nm
Transmittance at 500nm: 81%
Average refractive index (n _ave ): 1.525 (d line)
Dielectric constant (ε) determined 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 loss tangent (D _f ): 0.0026 (TE, 10 GHz), 0.0030 (TM, 10 GHz), 0.0031 (TE, 20 GHz)

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

6PFDA (0.363 g, 0.75 mmol), BisAAF (0.251 g, 0.75 mmol) and dehydrated NMP (3 mL) were placed in an eggplant flask (100 mL) equipped with a stirring bar, nitrogen introduction tube, and Dimroth condensing tube. Dissolved. 6PFDAH (0.891 g, 1.50 mmol) was added to this solution and dissolved with stirring at room temperature. Thereafter, by stirring at 60° C. for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.38 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). An NMP solution (20 wt%) of a fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Thereafter, a pale yellow and transparent fluorinated polyimide compound (6PFDA/ A film (film thickness: 45 μm) of BisAAF (50/50)-6PFDAH) was produced.
The properties of the obtained fluorinated polyimide compound film are shown below.
FT-IR (film, cm ^-1 ): 1786 (C=O), 1727 (C=O), 1373 (CN), 1199 (CF), 719 (CN)
Solubility: Insoluble in organic solvents such as NMP, DMAc, DMF, DMI, γ-butyrolactone, THF, chloroform, etc. Weight loss temperature: 525°C (in air), 545°C (in nitrogen)
10% weight loss temperature: 543℃ (in air), 561℃ (in nitrogen)
Carbonization yield: 55% (in nitrogen, 800°C)
Glass transition temperature: 175°C (DSC measurement), 170°C (DMA measurement), 174°C (TMA measurement)
Coefficient of thermal expansion (CTE): 94ppm/℃ (temperature range from 100℃ to 150℃, TMA measurement)
Cutoff wavelength: 347nm (UV-vis)
Transmittance at 500nm: 75% (UV-vis)
Average refractive index (n _ave ): 1.516 (d line)
Dielectric constant (ε) determined from refractive index: 2.53 (ε=1.10×n _ave ² )
Dielectric constant (D _k ): 2.43 (TE, 10 GHz), 2.49 (TM, 10 GHz), 2.46 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0013 (TE, 10 GHz), 0.0014 (TM, 10 GHz), 0.0014 (TE, 20 GHz)

<Example 4>
Fluorinated polyamide compound and fluorinated polyimide compound (6PFDA-6PFDAH/6FDA (50/50))

6PFDA (0.726 g, 1.50 mmol) and dehydrated NMP (3 mL) were placed in an eggplant flask (100 mL) equipped with a stirring bar, nitrogen inlet tube, and Dimroth condenser, and dissolved. 6PFDAH (0.446 g, 0.75 mmol) and 6FDA (0.333 g, 0.75 mmol) were added to this solution and dissolved with stirring at room temperature. Thereafter, by stirring at 60° C. for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.33 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). An NMP solution (20 wt%) of a fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Thereafter, a pale yellow and transparent fluorinated polyimide compound (6PFDA- A film (thickness: 34 μm) of 6PFDAH/6FDA (50/50) was produced.
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, chloroform, etc. Weight loss temperature: 507°C (in air), 524°C (in nitrogen)
10% weight loss temperature: 522℃ (in air), 542℃ (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): 103ppm/℃ (temperature range from 100℃ to 150℃, TMA measurement)
Cutoff wavelength: 363nm (UV-vis)
Transmittance at 500nm: 65% (UV-vis)
Average refractive index (n _ave ): 1.517 (d line)
Dielectric constant (ε) determined from refractive index: 2.53 (ε=1.10×n _ave ² )
Dielectric constant (D _k ): 2.48 (TE, 10 GHz), 2.49 (TM, 10 GHz), 2.49 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0017 (TE, 10 GHz), 0.0014 (TM, 10 GHz), 0.0019 (TE, 20 GHz)

<Example 5>
Fluorinated polyamide compound and fluorinated polyimide compound (BisAAF-4PFDAH)

BisAAF (0.501 g, 1.50 mmol) and dehydrated NMP (3 mL) were placed in an eggplant flask (100 mL) equipped with a stirring bar, nitrogen inlet tube, and Dimroth condenser, and dissolved. 4PFDAH (0.741 g, 1.50 mmol) was added to this solution and dissolved with stirring at room temperature. Thereafter, by stirring at 30° C. for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.37 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). An NMP solution (20 wt%) of a fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Thereafter, a pale yellow and transparent fluorinated polyimide compound (BisAAF- 4PFDAH) film (thickness: 32 μm) was prepared.
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 ( _Mn ): 38,000
Weight average molecular weight ( _Mw ): 114,000
Molecular weight distribution ( _Mw / _Mn ): 3.0
Solubility: 5% soluble in organic solvents such as NMP, DMAc, DMF, DMI, γ-butyrolactone, THF, chloroform, etc. Weight loss temperature: 504°C (in air), 529°C (in nitrogen)
10% weight loss temperature: 522℃ (in air), 545℃ (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): 77ppm/℃ (temperature range from 100℃ to 150℃, TMA measurement)
Average refractive index (n _ave ): 1.552 (d line)
Dielectric constant (ε) determined from refractive index: 2.65 (ε=1.10×n _ave ² )
Dielectric constant (D _k ): 2.57 (TE, 10 GHz), 2.52 (TM, 10 GHz), 2.55 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0047 (TE, 10 GHz), 0.0045 (TM, 10 GHz), 0.0049 (TE, 20 GHz)

<Example 6>
Fluorinated polyamide compound and fluorinated polyimide compound (m-6PFDA-6PFDAH)

Using m-6PFDA in place of 6PFDA in Example 1, the mixture was stirred in dehydrated NMP at 60° C. for 18 hours to obtain a viscous fluorinated polyamide compound. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.30 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). This NMP solution of the fluorinated polyamide compound was cast onto a glass plate, the temperature was raised stepwise to 250°C, and by heating at 250°C for 1 hour, a pale yellow and transparent fluorinated polyimide compound (m-6PFDA) was produced. -6PFDAH) film (thickness: 70 μm) was prepared.
The properties of the obtained fluorinated polyimide compound film are shown below.
5% weight loss temperature: 549℃ (in nitrogen)
10% weight loss temperature: 568℃ (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): 101ppm/℃ (temperature range from 50℃ to 80℃, TMA measurement)
Dielectric constant (D _k ): 2.39 (TE, 10 GHz), 2.43 (TM, 10 GHz), 2.35 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0019 (TE, 10 GHz), 0.0021 (TM, 10 GHz), 0.0017 (TE, 20 GHz)

<Example 7>
Fluorinated polyamide compound and fluorinated polyimide compound (TFMB-6PFDAH)

TFMB was used in place of BisAAF in Example 2, 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 _inh ) of the fluorinated polyamide compound was 0.82 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). This NMP solution of the fluorinated polyamide compound was cast onto a glass plate, the temperature was raised stepwise to 250°C, and by heating at 250°C for 1 hour, a pale yellow and transparent fluorinated polyimide compound (TFMB-6PFDAH) was obtained. ) film (thickness: 55 μm) was prepared.
The properties of the obtained fluorinated polyimide compound film are shown below.
5% weight loss temperature: 553℃ (in nitrogen)
10% weight loss temperature: 570℃ (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): 82ppm/℃ (temperature range from 140℃ to 180℃, TMA measurement)
Cutoff wavelength: 359nm (UV-vis)
Transmittance at 500nm: 78% (UV-vis)
Dielectric constant (D _k ): 2.47 (TE, 10 GHz), 2.59 (TM, 10 GHz), 2.51 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0017 (TE, 10 GHz), 0.0018 (TM, 10 GHz), 0.0021 (TE, 20 GHz)

<Example 8>
Fluorinated polyamide compound and fluorinated polyimide compound (BAFL-6PFDAH)

BAFL was used in place of BisAAF in Example 2, 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 _inh ) of the fluorinated polyamide compound was 0.43 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). The NMP solution of this fluorinated polyamide compound was cast onto a glass plate, the temperature was raised stepwise to 300°C, and by heating at 300°C for 1 hour, a pale yellow and transparent fluorinated polyimide compound (BAFL-6PFDAH) was produced. ) film (thickness: 60 μm) was prepared.
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, chloroform, etc. 5% weight loss temperature: 528°C (in nitrogen)
10% weight loss temperature: 547℃ (in nitrogen)
Glass transition temperature: 272°C (DSC measurement), 263°C (DMA measurement), 274°C (TMA measurement)
Coefficient of thermal expansion (CTE): 80ppm/℃ (temperature range from 150℃ to 200℃, TMA measurement)
Cutoff wavelength: 365nm (UV-vis)
Transmittance at 500nm: 86% (UV-vis)
Average refractive index (n _ave ): 1.591 (d line)
Dielectric constant (ε) determined from refractive index: 2.78 (ε=1.10×n _ave ² )
Dielectric constant (D _k ): 2.61 (TE, 10 GHz), 2.68 (TM, 10 GHz), 2.59 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0020 (TE, 10 GHz), 0.0022 (TM, 10 GHz), 0.0023 (TE, 20 GHz)

<Example 9>
Fluorinated polyamide compounds and fluorinated polyimide compounds (6PFDA-4PFDAH)

Using 6PFDA in place of BisAAF in Example 5, the mixture was stirred in dehydrated NMP at 60° C. for 18 hours to obtain a viscous fluorinated polyamide compound. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.38 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). This NMP solution of the fluorinated polyamide compound was cast onto a glass plate, the temperature was raised stepwise to 250°C, and by heating at 250°C for 1 hour, a pale yellow and translucent fluorinated polyimide compound (6PFDA- 4PFDAH) film (thickness: 80 μm) was prepared.
The properties of the obtained fluorinated polyimide compound film are shown below.
5% weight loss temperature: 532°C (in air), 529°C (in nitrogen)
10% weight loss temperature: 549℃ (in air), 545℃ (in nitrogen)
Carbonization yield: 52% (in nitrogen, 800°C)
Melting point: 330°C (DSC measurement)
Average refractive index (n _ave ): 1.551 (d line)
Dielectric constant (ε) determined from refractive index: 2.65 (ε=1.10×n _ave ² )
Dielectric constant ( _Dk ): 2.53 (TM, 10GHz)
Dielectric loss tangent (D _f ): 0.0025 (TM, 10GHz)

<Comparative example 1>
Fluorinated polyamide compounds and fluorinated polyimide compounds (BisAAF-6FDA)

BisAAF (0.501 g, 1.50 mmol) and dehydrated NMP (3 mL) were placed in an eggplant flask (100 mL) equipped with a stirring bar, nitrogen inlet tube, and Dimroth condenser, and dissolved. 6FDA (0.666 g, 1.50 mmol) was added to this solution and dissolved with stirring at room temperature. Thereafter, by stirring at 60° C. for 18 hours, a viscous solution of the fluorinated polyamide compound was obtained. The logarithmic viscosity (η _inh ) of the fluorinated polyamide compound was 0.58 dL/g (NMP solution with a concentration of 0.5 g/dL, measured at 30° C.). An NMP solution (20 wt%) of a fluorinated polyamide compound was prepared and cast onto a glass plate. This was dried under reduced pressure at room temperature for 3 hours. Then, by heating stepwise in a vacuum dryer for 6 hours at 60°C, 1 hour at 100°C, 1 hour at 200°C, 1 hour at 250°C, and 1 hour at 300°C, a pale yellow and transparent fluorine A film (thickness: 58 μm) of a polyimide compound (BisAAF-6FDA) was prepared.
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 ( _Mw ): 61,000
Molecular weight distribution (M _w /M _n ): 2.3
Solubility: 5% soluble in NMP, DMAc, DMF, DMI, γ-butyrolactone, THF, chloroform Weight loss temperature: 508°C (in air), 524°C (in nitrogen)
10% weight loss temperature: 525℃ (in air), 539℃ (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): 69ppm/℃ (temperature range from 100℃ to 150℃, TMA measurement)
Cutoff wavelength: 354nm
Transmittance at 500nm: 88%
Average refractive index (n _ave ): 1.550 (d line)
Dielectric constant (ε) determined from refractive index: 2.64 (ε=1.10×n _ave ² )
Dielectric constant (D _k ): 2.65 (TE, 10 GHz), 2.63 (TM, 10 GHz), 2.59 (TE, 20 GHz)
Dielectric loss tangent (D _f ): 0.0070 (TE, 10 GHz), 0.0053 (TM, 10 GHz), 0.0044 (TE, 20 GHz)

Claims (13)

1. A fluorinated polyamide compound having a repeating unit represented by formula (1).
   Formula (1):
   

   

   (In formula (1), n is an integer of 1 to 8, Ring A and Ring B are independently hydrocarbon rings with or without substituents, R is independently H, linear, branched A chain or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group, or a fluorine group with or without a substituent an aromatic group, L is a linking group, and R ¹ is independently OH, a linear or branched alkoxy group that may have a substituent, or a linear or branched alkoxy group that may have a substituent. Represents an aromatic oxy group or a halogen atom.)
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 compound according to any one of claims 1 to 3, wherein L is a single bond, -O-, -SO ₂ -, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group. Polyamide compound.
5. The fluorinated polyamide compound according to any one of claims 1 to 4, wherein the repeating unit represented by formula (1) is a repeating unit represented by formula (1-1).
   Formula (1-1):
   

   

   (In formula (1-1), n, L and R ¹ are as described above.)
6. A fluorinated polyimide compound having a repeating unit represented by formula (2).
   Formula (2):
   

   

   (In formula (2), n is an integer of 1 to 8, Ring A and Ring B are independently hydrocarbon rings with or without substituents, R is independently H, linear, branched A chain or cyclic aliphatic group, an aromatic group with or without a substituent, a linear, branched or cyclic fluorinated aliphatic group, or a fluorine group with or without a substituent aromatic group, L represents a linking group)
7. The fluorinated polyimide compound according to claim 6, 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. The fluorinated polyimide compound according to claim 6 or 7, 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. The fluorinated compound according to any one of claims 6 to 8, wherein L is a single bond, -O-, -SO ₂ -, -CO-, a divalent non-fluorinated organic group, or a divalent fluorinated organic group. Polyimide compound.
10. The fluorinated polyimide compound according to any one of claims 6 to 9, wherein the repeating unit represented by formula (2) is a repeating unit represented by formula (2-1).
    Formula (2-1):
    

    

    (In formula (2-1), n and L are as described above.)
11. The fluorinated polyimide compound according to any one of claims 6 to 10, which has a dielectric loss tangent (Df) of 0.005 or less at 10 GHz.
12. A low dielectric material containing the fluorinated polyamide compound according to any one of claims 1 to 5 or the fluorinated polyimide compound according to any one of claims 6 to 11.
13. A high-frequency electronic component containing the fluorinated polyamide compound according to any one of claims 1 to 5 or the fluorinated polyimide compound according to any one of claims 6 to 11.