WO2023219085A1 - Composé polyamide fluoré, composé polyimide fluoré, matériau faiblement diélectrique, composant électronique haute fréquence - Google Patents

Composé polyamide fluoré, composé polyimide fluoré, matériau faiblement diélectrique, composant électronique haute fréquence Download PDF

Info

Publication number
WO2023219085A1
WO2023219085A1 PCT/JP2023/017477 JP2023017477W WO2023219085A1 WO 2023219085 A1 WO2023219085 A1 WO 2023219085A1 JP 2023017477 W JP2023017477 W JP 2023017477W WO 2023219085 A1 WO2023219085 A1 WO 2023219085A1
Authority
WO
WIPO (PCT)
Prior art keywords
ring
fluorinated
formula
group
compound
Prior art date
Application number
PCT/JP2023/017477
Other languages
English (en)
Japanese (ja)
Inventor
好行 大石
大助 太田
Original Assignee
ダイキン工業株式会社
国立大学法人岩手大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ダイキン工業株式会社, 国立大学法人岩手大学 filed Critical ダイキン工業株式会社
Priority to JP2024520460A priority Critical patent/JPWO2023219085A1/ja
Publication of WO2023219085A1 publication Critical patent/WO2023219085A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • 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).
  • 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.
  • 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.)
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.)
  • fluorinated polyamide compound examples 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.
  • 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.
  • 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
  • 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.
  • 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 ⁇ 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 ⁇ 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 ⁇ 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.
  • 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. .
  • 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).
  • fluorinated polyimide compound examples 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).
  • 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.
  • 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 ⁇ 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 ⁇ 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 ⁇ inh ln (solution viscosity/solvent viscosity)/solution concentration
  • 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 (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.)
  • a compound (3-1) represented by the formula (3-1) is preferable.
  • a compound (4-1) represented by the formula (4-1) is preferable.
  • 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.
  • solvents include, but are not limited to, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP),
  • DMSO dimethyl sulfoxide
  • DMF N,N-dimethylformamide
  • DMAc N,N-dimethylacetamide
  • NMP N-methyl-2-pyrrolidone
  • Examples include 1,3-dimethylimidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropylene urea (DMPU), cyclohexanone, cyclopentanone, sulfolane, tetrahydrofuran (THF), and acetone.
  • N-methyl-2-pyrrolidone (NMP) and 1,3-dimethylimidazolidone (DMI) are preferred.
  • the amount of these solvents used is usually 100 to 1000
  • Polymerization can also be carried out in the presence of additives.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a fluorinated polyimide compound having a repeating unit represented by formula (2) is provided.
  • 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 fluoren
  • 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.
  • 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.
  • GPC Tosoh Corporation high-speed GPC system HLC-8220GPC (column: Tosoh TSKgel ( ⁇ -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
  • ⁇ 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.
  • 6PFDAH 4,4'-(1,6-perfluorohexylene)diphthalic anhydride
  • 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 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.
  • 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.
  • 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 ( ⁇ 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 ⁇ m) was prepared.
  • 6PFDA -6PFDAH 6PFDA -6PFDAH
  • 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.
  • BisAAF-6PFDAH fluorinated polyimide compound
  • the logarithmic viscosity ( ⁇ 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 ⁇ m) was prepared.
  • the properties of the obtained fluorinated polyimide compound film are shown below.
  • the logarithmic viscosity ( ⁇ 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 ⁇ m) of BisAAF (50/50)-6PFDAH) was produced.
  • the properties of the obtained fluorinated polyimide compound film are shown below.
  • the logarithmic viscosity ( ⁇ 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 ⁇ m) of 6PFDAH/6FDA (50/50) was produced.
  • the properties of the obtained fluorinated polyimide compound film are shown below.
  • 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.
  • BisAAF-4PFDAH fluorinated polyimide compound
  • the logarithmic viscosity ( ⁇ 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 ⁇ m) was prepared.
  • the properties of the obtained fluorinated polyimide compound film are shown below.
  • 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 ( ⁇ 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.).
  • 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 ( ⁇ 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.).
  • 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 ( ⁇ 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.).
  • the logarithmic viscosity ( ⁇ 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 ⁇ m) of a polyimide compound (BisAAF-6FDA) was prepared.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention fournit un composé polyimide fluoré ainsi qu'un composé polyamide fluoré possédant une unité de répétition spécifique.
PCT/JP2023/017477 2022-05-09 2023-05-09 Composé polyamide fluoré, composé polyimide fluoré, matériau faiblement diélectrique, composant électronique haute fréquence WO2023219085A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024520460A JPWO2023219085A1 (fr) 2022-05-09 2023-05-09

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022-077266 2022-05-09
JP2022077266 2022-05-09
JP2022-077810 2022-05-10
JP2022077810 2022-05-10

Publications (1)

Publication Number Publication Date
WO2023219085A1 true WO2023219085A1 (fr) 2023-11-16

Family

ID=88730269

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/017477 WO2023219085A1 (fr) 2022-05-09 2023-05-09 Composé polyamide fluoré, composé polyimide fluoré, matériau faiblement diélectrique, composant électronique haute fréquence

Country Status (2)

Country Link
JP (1) JPWO2023219085A1 (fr)
WO (1) WO2023219085A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02208324A (ja) * 1989-02-08 1990-08-17 Nitto Denko Corp 低誘電率シート、該シートを用いてなる積層板および多層回路基板
JPH04288344A (ja) * 1991-03-18 1992-10-13 Sanyo Chem Ind Ltd 保護用フィルム、保護層を有する部材
JP2021178956A (ja) * 2020-05-11 2021-11-18 ダイキン工業株式会社 フッ素化アミド化合物、フッ素化含窒素複素環含有化合物およびフッ素化化合物
JP2021178955A (ja) * 2020-05-11 2021-11-18 ダイキン工業株式会社 アミド化合物、含窒素複素環含有化合物および架橋物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02208324A (ja) * 1989-02-08 1990-08-17 Nitto Denko Corp 低誘電率シート、該シートを用いてなる積層板および多層回路基板
JPH04288344A (ja) * 1991-03-18 1992-10-13 Sanyo Chem Ind Ltd 保護用フィルム、保護層を有する部材
JP2021178956A (ja) * 2020-05-11 2021-11-18 ダイキン工業株式会社 フッ素化アミド化合物、フッ素化含窒素複素環含有化合物およびフッ素化化合物
JP2021178955A (ja) * 2020-05-11 2021-11-18 ダイキン工業株式会社 アミド化合物、含窒素複素環含有化合物および架橋物

Also Published As

Publication number Publication date
JPWO2023219085A1 (fr) 2023-11-16

Similar Documents

Publication Publication Date Title
US8101248B2 (en) Composition for forming substrate, and prepreg and substrate using the same
CN102604156A (zh) 碱产生剂
US20230099704A1 (en) Fluorinated amide compound, compound containing fluorinated nitrogen-containing heterocyclic ring, and fluorinated compound
JP2001114893A (ja) ポリベンゾオキサゾール樹脂およびその前駆体
Zhou et al. Soluble fluorinated polyimides derived from 1, 4‐(4′‐aminophenoxy)‐2‐(3′‐trifluoromethylphenyl) benzene and aromatic dianhydrides
JP7085737B2 (ja) ポリベンゾイミダゾール、その前駆体ポリアミド及びそれらの製造方法
Liu et al. Synthesis and characterization of new polybenzimidazopyrrolones derived from pyridine‐bridged aromatic tetraamines and dianhydrides
US20240092971A1 (en) Fluorine-containing polyether compound
US6054554A (en) Soluble polyimide resin comprising polyalicyclic structure
JP2021178955A (ja) アミド化合物、含窒素複素環含有化合物および架橋物
US6342638B1 (en) Triarylphosphine oxide derivatives containing fluorine substituents
WO2023219085A1 (fr) Composé polyamide fluoré, composé polyimide fluoré, matériau faiblement diélectrique, composant électronique haute fréquence
JP4176074B2 (ja) ビスフェニル−２，３，５，６−テトラフルオロ−４−トリフルオロメチルフェニルホスフィンオキシド誘導体およびその製造方法
CN108997580B (zh) 一种含蒽酮和三氟甲基结构的聚醚酰亚胺及其制备方法
WO2021033655A1 (fr) Composition de matériau de départ pour résine
KR101509316B1 (ko) 폴리이미드, 이의 제조방법 및 상기 폴리이미드를 포함하는 필름
WO2023022123A1 (fr) Composé polyamide contenant du fluor et polybenzoxazole contenant du fluor
JP6462236B2 (ja) ポリイミドおよび耐熱性フィルム
Wan et al. New polytriazoleimides with high thermal and chemical stabilities
JP4273981B2 (ja) アミノフェノール化合物、熱硬化性樹脂およびその製造法
CN115637020A (zh) 一种超支化环氧树脂热固性树脂组合物及其应用
JP2024068058A (ja) 変性ビスマレイミド樹脂
KR20210003609A (ko) 산무수물 화합물 제조방법, 이를 이용한 산무수물 화합물, 폴리이미드계 고분자, 고분자 필름, 및 디스플레이 장치용 기판
Liu et al. Synthesis and characterization of polybenzimidazopyrrolones based on pyridine-bridged aromatic tetraamines and dianhydrides
JP2011016969A (ja) 液状ポリイミド組成物及びポリイミド膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23803562

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024520460

Country of ref document: JP