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WO2025013869A1 - Polymère contenant du fluor ayant un cycle aromatique contenant de l'azote, son procédé de production et composition associée - Google Patents

Polymère contenant du fluor ayant un cycle aromatique contenant de l'azote, son procédé de production et composition associée Download PDF

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Publication number
WO2025013869A1
WO2025013869A1 PCT/JP2024/024818 JP2024024818W WO2025013869A1 WO 2025013869 A1 WO2025013869 A1 WO 2025013869A1 JP 2024024818 W JP2024024818 W JP 2024024818W WO 2025013869 A1 WO2025013869 A1 WO 2025013869A1
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group
fluoropolymer
nitrogen
fluorine
atom
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Japanese (ja)
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悠希 鈴木
義人 田中
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof

Definitions

  • This disclosure relates to a fluoropolymer having a nitrogen-containing aromatic ring, a method for producing the same, and a composition thereof.
  • Fluoropolymers are used in a variety of fields due to their properties such as transparency, durability, chemical resistance, and stability. For example, their use is being considered as resins for sealing light-emitting elements, insulating films for electrowetting devices, pellicle films that make up pellicles used to prevent foreign matter from adhering to photomasks and reticles in the manufacturing process of semiconductor devices and liquid crystal display panels, and adhesives for bonding the pellicle film to the frame that makes up the pellicle (Patent Documents 1-8).
  • the main object of the present disclosure is to provide a fluorine-containing polymer having a nitrogen-containing aromatic ring, a method for producing the same, a composition thereof, etc.
  • a functional group into a fluoropolymer terminal
  • the terminal is converted to -COF, and then the COF is hydrolyzed.
  • hydrogen fluoride is by-produced during the -COF conversion and subsequent hydrolysis, and this hydrogen fluoride dissolves in the water used for hydrolysis to produce aqueous hydrofluoric acid.
  • the main object of the present disclosure is to provide a method for producing a fluoropolymer having a functional terminal, in which the by-production of aqueous hydrofluoric acid is suppressed.
  • Item 2 The fluorine-containing polymer according to item 1, wherein the nitrogen-containing aromatic ring (3) is at least one selected from the group consisting of nitrogen-containing aromatic rings represented by the formula: Item 3.
  • Item 3. The fluorine-containing polymer according to Item 1 or 2, wherein the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from the group consisting of pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indolizine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzisoxazole, thiazole, isothiazole, benzothiazole, benzisothiazole, and purine.
  • Item 4. The fluorine-containing polymer according to item 1 or 2, wherein the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from the group consisting of imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole, and purine.
  • Item 5. Item 5.
  • the monomer unit contained as a main component in the fluoropolymer is The following formula (A1): [In the formula, R 1 represents a fluorine atom or a C1-C5 perfluoroalkyl group.] Monomer unit (A1) represented by the formula: The following formula (A2): [In the formula, R 2 to R 5 each independently represent a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.] or a monomer unit (A2) represented by the following formula (A3): [In the formula, R 6 to R 9 each independently represent a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.] Monomer unit (A3) represented by the following formula: Item 6.
  • the fluoropolymer according to Item 5 wherein Item 7.
  • Item 7. A fluoropolymer according to Item 6, wherein the monomer unit contained as a main component in the fluoropolymer is the monomer unit (A3).
  • Item 8. The monomer unit contained as a main component in the fluoropolymer is The following formula (A1-1): Monomer unit (A1-1) represented by the following formula: The following formula (A2-1): Monomer unit (A2-1) represented by the following formula: The following formula (A2-2): or a monomer unit represented by the following formula (A3-1): Monomer unit (A3-1) represented by the following formula: Item 7.
  • the linker has the following formula (L): [In the formula, v is 0 or 1, A is an oxygen atom, a sulfur atom, -O-CH 2 -, or a nitrogen atom bonded to a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group, and * indicates the side bonded to the nitrogen-containing aromatic ring.]
  • Item 3 The fluoropolymer according to item 2, which has a structure represented by the following formula: Item 14.
  • Item 13 The fluoropolymer according to any one of Items 1 to 12, wherein the nitrogen-containing aromatic ring is bonded to one or two of the monomer units at the ends of the main chain of the fluoropolymer.
  • a method for producing a fluorine-containing polymer containing a monomer unit having a fluorine-containing aliphatic ring as a main component and having a nitrogen-containing aromatic ring comprising the steps of: the process comprises a step of reacting a fluorine-containing polymer (A) containing as a main component a monomer unit having a fluorine-containing aliphatic ring with a reactive reagent (B) having a nitrogen-containing aromatic ring in a solvent (C), the fluorine-containing aliphatic ring has 1, 2 or 3 etheric oxygen atoms as ring-constituting atoms, and when the fluorine-containing aliphatic ring contains a plurality of the etheric oxygen atoms, the etheric oxygen atoms are not adjacent to each other; A method for producing a fluorine-containing polymer.
  • the nitrogen-containing aromatic ring is The following formula (1): [A represents an oxygen atom, a sulfur atom, or a nitrogen atom which may be substituted with a substituent R 10 , R 10 represents a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group, Any one of X 1 to X 4 represents a carbon atom, and the other Xs each independently represent a nitrogen atom or a carbon atom; at least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when there are a plurality of carbon atoms, is independently bonded to the main chain of the fluorine-containing polymer directly or via a linker; Other carbon atoms constituting the nitrogen-containing aromatic ring, when there are multiple carbon atoms, may each independently have a substituent, the substituents, when present in plurality, are each independently a fluorine atom, a hydroxy
  • a nitrogen-containing aromatic ring (2) represented by the following formula (3):
  • R 20 represents a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group
  • Any one of Z 1 to Z 8 represents a carbon atom, and the other Zs each independently represent a nitrogen atom or a carbon atom; at least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when there are a plurality of carbon atoms, is independently bonded to the main chain of the fluorine-containing polymer directly or via a linker;
  • Other carbon atoms constituting the nitrogen-containing aromatic ring, when there are multiple carbon atoms may each independently have a substituent, the substituents, when present in plurality, are each independently a fluorine atom, a hydroxyl group
  • Item 17 The method for producing a fluorine-containing polymer according to Item 16, wherein the nitrogen-containing aromatic ring (3) is at least one selected from the group consisting of Item 18.
  • Item 18 The method for producing a fluorine-containing polymer according to Item 16 or 17, wherein the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from the group consisting of pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indolizine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzisoxazole, thiazole, isothiazole, benzothiazole, benzisothiazole, and purine.
  • Item 19 The method for producing a fluorine-containing polymer according to Item 16 or 17, wherein the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from the group consisting of imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole, and purine.
  • the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from the group consisting of imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole, and purine.
  • the reactive reagent (B) is 1-(3-aminopropyl)imidazole, 4-(1H-benzimidazol-2-yl)aniline, 2-aminobenzimidazole, 5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, 3-amino-1H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1-aminobenzotriazole, 2-aminobenzotriazole, 1H-1,2,3-benzotriazole-5-amine, 5-amino Benzotriazole, melamine monomer, 2-methoxy-4-methyl-6-(methylamino)-1,3,5-triazine, 2,4-diamino-6-butylamino-1,3,5-triazine, 2-amino-4-methoxy-6-methyl-1,
  • tert-butyl-5-hydroxybenzoxazole is at least one member selected from the group consisting of 1H-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 1H-benzotriazole-1-methanol, 2-aminooxazole, 5-amino-3-methylisoxazole, 3-hydroxy-5-methylisoxazole, muscimol, 3-amino-5-tert-butylisoxazole, 2-aminobenzoxazole, and 2-mercaptobenzoxazole.
  • Item 21 is at least one member selected from the group consisting of 1H-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 1H-benzotriazole-1-methanol, 2-aminooxazole, 5-amino-3-methylisoxazole, 3-hydroxy-5-methylisoxazole,
  • the monomer unit contained as a main component in the fluoropolymer (A) is The following formula (A1): [In the formula, R 1 represents a fluorine atom or a C1-C5 perfluoroalkyl group.] Monomer unit (A1) represented by: The following formula (A2): [In the formula, R 2 to R 5 each independently represent a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.] or a monomer unit (A2) represented by the following formula (A3): [In the formula, R 6 to R 9 each independently represent a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.] Monomer unit (A3) represented by the following formula: Item 21.
  • Item 24. The process for producing a fluoropolymer according to Item 23, wherein the monomer unit contained as a main component in the fluoropolymer (A) is the monomer unit (A3-1).
  • Item 25. The method for producing a fluoropolymer according to any one of Items 16 to 24, wherein the solvent (C) is an aprotic solvent.
  • the aprotic solvent is at least one solvent selected from the group consisting of perfluoroaromatic compounds, perfluorotrialkylamines, perfluoroalkanes, hydrofluorocarbons, perfluorocyclic ethers, hydrofluoroethers, and olefin compounds containing at least one chlorine atom.
  • the aprotic solvent is a hydrofluoroether.
  • the aprotic solvent is Formula (C-1): F(CF 2 ) p O(CH 2 ) q H (C-1) [In the formula, p is an integer from 1 to 6, and q is an integer from 1 to 4.]
  • the aprotic solvent is represented by formula (C-5): R 21 -O-R 22 (C-5) [In the formula, R 21 is linear or branched propyl or butyl in which one or more hydrogen atoms are substituted with fluorine atoms, and R 22 is methyl or ethyl.] Item 26.
  • Item 31. The method for producing a fluoropolymer according to any one of Items 16 to 30, wherein the mass average molecular weight of the fluoropolymer is within the range of 5,000 to 2,000,000.
  • Item 31. The method for producing a fluoropolymer according to any one of Items 16 to 30, wherein the mass average molecular weight of the fluoropolymer is within the range of 10,000 to 1,500,000.
  • the fluoropolymer (A) comprises a COF group and a fluoropolymer having the following formula (K): [In the formula, v represents 0 or 1, and R 40 represents an alkyl group or an alkoxy group.]
  • Item 33 The method for producing a fluorinated polymer according to any one of items 16 to 32, wherein the fluorinated polymer (K) has at least one group selected from the group consisting of groups represented by the following formula (1): Item 34. Item 34.
  • a fluoropolymer containing the monomer unit having a fluorinated aliphatic ring as a main component and having a nitrogen-containing aromatic ring one of the carbon atoms constituting the nitrogen-containing aromatic ring is bonded via a linker to one or two of the monomer units at the terminals of the main chain of the fluoropolymer,
  • the structure of the linker and the nitrogen-containing aromatic ring bonded to one or two of the terminal monomer units of the main chain of the fluoropolymer is represented by the following formula: and
  • the reactive reagent (B) is represented by the following formula: Any compound represented by the formula:
  • the monomer unit contained as a main component in the fluoropolymer (A) is The following formula (A3-1):
  • the monomer unit (A3-1) is represented by the following formula: the terminal structure of the fluoropolymer (A) is -COF or -CF 2 -O-CO-O-normal propyl;
  • Item 36 Item 16.
  • An encapsulating resin comprising the fluorine-containing polymer according to any one of items 1 to 15.
  • Item 37 Item 16.
  • a fluororesin adhesive comprising the fluorine-containing polymer according to any one of items 1 to 15.
  • Item 38 Item 38.
  • the fluororesin adhesive according to item 37 which is for bonding a pellicle membrane to a frame.
  • Item 39 Item 37.
  • An optical device comprising the sealing resin according to item 36, the fluororesin adhesive according to item 37, or the fluororesin adhesive according to item 38.
  • Item 40 Item 16.
  • a pellicle comprising a pellicle membrane and a frame, the pellicle comprising the fluoropolymer according to any one of Items 1 to 15.
  • Item 41. A pellicle according to item 40, wherein the pellicle membrane and the frame are bonded with the fluororesin adhesive according to item 37.
  • Item 42. Item 41.
  • Item 43. Item 43. The exposure method according to item 42, wherein the light source having a wavelength of 200 nm or less is a fluorine gas excimer laser or a fluorine gas excimer laser.
  • a composition comprising the fluorine-containing polymer according to any one of items 1 to 15 and hydrogen fluoride, The composition, wherein the content of said hydrogen fluoride is 0.005 ppm to 50 ppm relative to the content of said fluoropolymer.
  • Item 45. The composition according to item 44, wherein the content of said hydrogen fluoride is 0.005 ppm to 10 ppm based on the content of said fluoropolymer.
  • a fluoropolymer having improved adhesion to metals According to the present disclosure, it is possible to provide a method for producing a fluoropolymer in which the by-production of hydrogen fluoride is suppressed. According to the present disclosure, it is possible to provide a fluoropolymer-containing composition having a low hydrogen fluoride content and useful as a source of a fluoropolymer.
  • a "fluorine-containing alicyclic ring” has, as ring-constituting atoms, a plurality of carbon atoms and 1, 2 or 3 ethereal oxygen atoms.
  • a "fluorine-containing alicyclic ring” contains, as ring-constituting atoms, a plurality of oxygen atoms, the oxygen atoms are not adjacent to each other.
  • the term "fluorine-containing aliphatic ring” includes a saturated aliphatic monocyclic ring containing a fluorine atom.
  • the number of substituents can be one or more, and can be, for example, 1 to 4, 1 to 3, 1 to 2, 1, 2, 3, or 4.
  • the ring-constituting carbon atoms may have either or both of a fluorine atom and a substituent.
  • fluorine-containing aliphatic ring examples include perfluorooxetane which may have one or more substituents, perfluorotetrahydrofuran which may have one or more substituents, perfluorodioxolane which may have one or more substituents, perfluorotetrahydropyran which may have one or more substituents, perfluoro-1,3-dioxane which may have one or more substituents, perfluorooxepane which may have one or more substituents, perfluoro-1,3-dioxepane which may have one or more substituents, perfluoro-1,4-dioxepane which may have one or more substituents, and perfluoro-1,3,5-trioxepane which may have one or more substituents.
  • alkyl groups in this specification include linear or branched C1-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • the alkyl group can be a C1-C6 alkyl group, a C1-C5 alkyl group, a C1-C4 alkyl group, or a C1-C3 alkyl group.
  • the alkyl group may or may not contain a C1-C5 ether bond.
  • the alkyl group containing a C1-C5 ether bond may be an alkyl group containing a C1-C4 ether bond, an alkyl group containing a C1-C3 ether bond, an alkyl group containing a C2-C5 ether bond, or an alkyl group containing a C3-C5 ether bond.
  • alkyl groups containing C1-C5 ether bonds are CH 3 OCH 2 -, CH 3 CH 2 OCH 2 -, CH 3 OCH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 CH 2 -, CH 3 CH 2 CH 2 CH 2 OCH 2 -, CH 3 CH 2 CH 2 OCH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 CH 2 -, CH 3 CH 2 OCH 2 CH 2 CH 2 -, CH 3 OCH(CH 3 )-, CH 3 CH(CH 3 )OCH 2 -, CH 3 CH 2
  • These can include OCH(CH 3 )-, CH 3 OC(CH 3 ) 2 -, and CH 3 OCH 2 CH 2 OCH 2 -.
  • a “fluoroalkyl group” is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the "fluoroalkyl group” may be a straight-chain or branched fluoroalkyl group.
  • the "fluoroalkyl group” can have, for example, 1 to 12, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 6, 5, 4, 3, 2, or 1 carbon atom.
  • the number of fluorine atoms in the "fluoroalkyl group” can be 1 or more (for example, 1 to 3, 1 to 5, 1 to 9, 1 to 11, or 1 to the maximum number that can be substituted).
  • fluoroalkyl group examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group (CF 3 --), a 2,2,2-trifluoroethyl group (CF 3 CH 2 --), a perfluoroethyl group (C 2 F 5 --), a tetrafluoropropyl group (e.g., HCF 2 CF 2 CH 2 --), a hexafluoropropyl group (e.g., (CF 3 ) 2 CH-), a perfluorobutyl group (e.g., CF 3 CF 2 CF 2 --), an octafluoropentyl group (e.g., HCF 2 CF 2 CF 2 CH 2 --), a perfluoropentyl group (e.g., CF 3 CF 2 CF 2 CF 2 --), and a perfluorohexyl group (e.g.,
  • an "alkoxy group” can be a group represented by RO--, where R is an alkyl group (e.g., a C1-C10 alkyl group).
  • alkoxy groups include straight-chain or branched C1-C10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy.
  • a “fluoroalkoxy group” is an alkoxy group in which at least one hydrogen atom is replaced with a fluorine atom.
  • the "fluoroalkoxy group” may be a linear or branched fluoroalkoxy group.
  • the "fluoroalkoxy group” can have, for example, 1 to 12, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 6, 5, 4, 3, 2, or 1 carbon atom.
  • the number of fluorine atoms in the "fluoroalkoxy group” can be 1 or more (for example, 1 to 3, 1 to 5, 1 to 9, 1 to 11, or 1 to the maximum number that can be substituted).
  • the term “fluoroalkoxy group” encompasses a perfluoroalkoxy group.
  • perfluoroalkoxy group is an alkoxy group in which all of the hydrogen atoms have been replaced with fluorine atoms.
  • perfluoroalkoxy groups include a trifluoromethoxy group (CF 3 O--), a pentafluoroethoxy group (C 2 F 5 O--), a heptafluoropropyloxy group (CF 3 CF 2 CF 2 O--), and a heptafluoroisopropyloxy group ((CF 3 ) 2 CFO--).
  • fluoroalkoxy group examples include a monofluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group (CF 3 CH 2 O-), a perfluoroethoxy group (C 2 F 5 O-), a tetrafluoropropyloxy group (e.g., HCF 2 CF 2 CH 2 O-), a hexafluoropropyloxy group (e.g., (CF 3 ) 2 CHO-), a perfluorobutyloxy group (e.g., CF 3 CF 2 CF 2 O-), an octafluoropentyloxy group (e.g., HCF 2 CF 2 CF 2 CH 2 O-), a perfluoropentyloxy group (e.g., CF 3 CF 2 CF 2 CH 2 O-), and a perfluorohe
  • a "nitrogen-containing aromatic ring” has at least one nitrogen atom and at least one carbon atom as ring-constituting atoms.
  • the number of nitrogen atoms constituting the ring can be, for example, 1, 2, 3, 4, 5, 6, etc., but does not exceed the number of ring-constituting atoms minus 1.
  • the ring-constituting atoms other than the ring-constituting nitrogen atom may all be carbon atoms, or may be at least one carbon atom and other atoms.
  • the number of ring-constituting carbon atoms can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, etc., but does not exceed the number of ring-constituting atoms minus 1.
  • At least one (preferably 1 or 2, more preferably 1) ring-constituting carbon atom, when there are a plurality of ring-constituting carbon atoms, is preferably independently bonded to the main chain of the fluorine-containing polymer via a linker or directly.
  • the other ring-constituting atom may be an oxygen atom, a sulfur atom, etc., and is preferably an oxygen atom or a sulfur atom.
  • the number of other ring-constituting atoms may be, for example, 1 or 2, etc., and is preferably 1.
  • the ring-constituting atoms may have a substituent.
  • the substituent may be a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, an alkyl group, or the like.
  • the number of the substituents may be, for example, 1, 2, 3, 4, or the like. When there are a plurality of the substituents, they may be the same or different.
  • substituents include a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, an alkyl group, or the like.
  • the "nitrogen-containing aromatic ring” may have an oxygen atom or a sulfur atom as another ring-constituting atom. The number of other ring-constituting atoms may be 1 or 2, etc., and is preferably 1.
  • the "nitrogen-containing aromatic ring” includes an aromatic monocyclic ring containing at least one nitrogen atom.
  • the "nitrogen-containing aromatic ring” includes a ring having 4 or more members (e.g., a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring).
  • Examples of the ring structure that is the basis of the "nitrogen-containing aromatic ring” include pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indolizine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzisoxazole, thiazole, isothiazole, benzothiazole, benzisothiazole, and purine, and imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole,
  • these rings are bonded to the main chain of the fluorine-containing polymer at the ring-constituting carbon atom.
  • the ring-constituting atoms of these rings may have a substituent.
  • Fluorine-containing polymer having a nitrogen-containing aromatic ring One embodiment of the present disclosure is a fluorine-containing polymer having a nitrogen-containing aromatic ring.
  • the fluorine-containing polymer is soluble in a solvent (preferably an aprotic solvent).
  • the polymerization site of the monomer constituting the polymer is a carbon atom.
  • the polymerization site of the monomer constituting the fluorine-containing polymer is a site formed by bonding the monomer with another monomer during polymerization. Typically, it is a site where a monomer unit is bonded to another monomer unit.
  • the fluoropolymer has a nitrogen-containing aromatic ring in its structure.
  • the nitrogen-containing aromatic rings may be the same or different.
  • the nitrogen-containing aromatic ring may be included in the main chain or in the side chain of the fluoropolymer.
  • the fluoropolymer of the present disclosure has a nitrogen-containing aromatic ring in its structure, and thus has high adhesion to metals.
  • the ring-constituting carbon atom of the nitrogen-containing aromatic ring is preferably bonded to the main chain of the fluoropolymer via a linker or directly, more preferably bonded to the main chain of the fluoropolymer via a linker.
  • the nitrogen-containing aromatic ring may be bonded to a monomer unit at the end of the main chain of the fluoropolymer, or may be bonded to a monomer unit that is not at the end of the main chain.
  • the nitrogen-containing aromatic ring may be bonded to one or two of the monomer units at the end of the main chain of the fluoropolymer.
  • the linker may be, for example, a linker represented by the following formula (L): [In the formula, v is 0 or 1, A is an oxygen atom, a sulfur atom, -O-CH 2 -, or a nitrogen atom bonded to a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group, and * indicates the side bonded to the nitrogen-containing aromatic ring.]
  • the structure may be represented by the following formula: A may be an oxygen atom, a sulfur atom, -O-CH 2 -, or a nitrogen atom bonded to a hydrogen atom, or it may be a sulfur atom, -O-CH 2 -, or a nitrogen atom bonded to a hydrogen atom.
  • the linker may be -CO-NH-*, -CF 2 -O-CO-NH-*, or -CO-S-* (in these chemical structures, * indicates the side attached to the nitrogen-
  • Ring structures that serve as the basis of the nitrogen-containing aromatic ring include, for example, pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indolizine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzisoxazole, thiazole, isothiazole, benzothiazole, benzisothiazole, and purine, of which pyrazole, imidazole, triazole, oxazole, isoxazole, pyridazine, pyrimidine, triazine, benzimidazole, benzotriazole, benzothiazole, and purine are preferred, and imidazole, triazole, triazine, benzimidazole, benzotriazole, benzo
  • the nitrogen-containing aromatic ring is, for example, a ring represented by the following formula (1): [A represents an oxygen atom, a sulfur atom, or a nitrogen atom which may be substituted with a substituent R 10 , R 10 represents a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group, any one of X 1 to X 4 represents a carbon atom, and the other Xs independently represent a nitrogen atom or a carbon atom, at least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when there are a plurality of them, is independently bonded to the main chain of the fluorine-containing polymer via a linker or directly, and the other carbon atoms constituting the nitrogen-containing aromatic ring, when there are a plurality of them, may independently have a substituent, and the substituent, when there are a plurality of them, is independently a flu
  • At least one of A and X 1 to X 4 is a nitrogen atom.
  • the number of nitrogen atoms in A and X 1 to X 4 may be 1, 2, or 3.
  • the number of carbon atoms in A and X 1 to X 4 may be 2, 3, or 4. It is preferable that A and X 1 to X 4 are composed of a nitrogen atom and a carbon atom.
  • the ring structure that is the basis of the nitrogen-containing aromatic ring (1) can be, for example, pyrrole, pyrazole, imidazole, triazole, oxazole, isoxazole, thiazole, isothiazole, etc., and may be pyrazole, imidazole, triazole, oxazole, isoxazole, etc., or may be imidazole, triazole, oxazole, isoxazole, etc.
  • At least one of Y 1 to Y 6 is a nitrogen atom.
  • the number of nitrogen atoms in Y 1 to Y 6 may be 1, 2, or 3.
  • the number of carbon atoms in Y 1 to Y 6 may be 3, 4, or 5. It is preferable that Y 1 to Y 6 are composed of a nitrogen atom and a carbon atom.
  • Examples of the ring structure that serves as the basis of the nitrogen-containing aromatic ring (2) include pyridine, pyridazine, pyrimidine, pyrazine, triazine, etc., and may be pyridazine, pyrimidine, triazine, etc., or may be triazine.
  • B and at least one of Z 1 to Z 8 are nitrogen atoms. It is preferred that at least one of B, Z 1 and Z 2 is a nitrogen atom, and Z 3 to Z 8 are all carbon atoms.
  • the number of nitrogen atoms in Z 1 to Z 8 may be 1, 2 or 3.
  • the number of carbon atoms in Z 1 to Z 8 may be 5, 6 or 7. It is preferred that B and Z 1 to Z 8 are composed of nitrogen atoms and carbon atoms.
  • the ring structure that is the basis of the nitrogen-containing aromatic ring (3) includes, for example, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, purine, etc., and may be benzimidazole, benzotriazole, benzothiazole, purine, etc., or may be benzimidazole, benzotriazole, purine, etc.
  • R 10 may be a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group, or may be a hydroxyl group, a mercapto group, or an alkyl group.
  • R 10 When R 10 is an alkyl group, it may contain a C1-C5 ether bond, for example, CH 3 OCH 2 -, CH 3 CH 2 OCH 2 -, CH 3 OCH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 CH 2 OCH 2 CH 2 -, CH 3 CH 2 OCH 2 CH 2 CH 2 -, CH 3 OCH(CH 3 )-, CH 3 CH(CH 3 )OCH 2 -, CH It may be CH 3 OCH (CH 3 )-, CH 3 OC(CH 3 ) 2 -, and CH 3 OCH 2 CH 2 OCH 2 -.
  • R 20 may be a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group, or may be a hydroxyl group, a mercapto group, or an alkyl group.
  • R 20 When R 20 is an alkyl group, it may contain a C1-C5 ether bond, for example, CH 3 OCH 2 -, CH 3 CH 2 OCH 2 -, CH 3 OCH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 CH 2 OCH 2 CH 2 -, CH 3 CH 2 OCH 2 CH 2 CH 2 -, CH 3 OCH(CH 3 )-, CH 3 CH(CH 3 )OCH 2 -, CH It may be CH 3 OCH (CH 3 )-, CH 3 OC(CH 3 ) 2 -, and CH 3 OCH 2 CH 2 OCH 2 -.
  • the ring-constituting carbon atoms may have a substituent.
  • the substituent may be a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, an alkyl group, or the like; a hydroxyl group, a mercapto group, a cyano group, an alkyl group, or the like; a hydroxyl group, a mercapto group, an alkyl group, or the like;
  • the substituent is an alkyl group, it may contain a C1-C5 ether bond, for example, CH 3 OCH 2 -, CH 3 CH 2 OCH 2 -, CH 3 OCH 2 CH 2 -, CH 3 CH 2 CH 2 OCH 2 -, CH 3 CH 2 OCH 2 CH 2 -, CH 3 OCH 2 CH 2 CH 2 -, CH 3 CH 2 CH 2 CH 2 OCH 2 -, CH 3 CH 2 CH 2 CH 2 OCH 2
  • the number of substituents on the ring-constituting carbon atoms can be 0 to 3, 0 to 2, 0 or 1, or 0.
  • the number of substituents on the ring-constituting carbon atoms can be 0 to 4, 0 to 3, 0 to 2, 0 or 1, or 0.
  • the number of substituents on the ring-constituting carbon atoms can be 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 or 1, or 0.
  • a fluoropolymer having a nitrogen-containing aromatic ring In a fluoropolymer having a nitrogen-containing aromatic ring, one of the carbon atoms constituting the nitrogen-containing aromatic ring is bonded to one or two of the monomer units at the ends of the main chain of the fluoropolymer via a linker, and the structure of the linker and the nitrogen-containing aromatic ring bonded to one or two of the monomer units at the ends of the main chain of the fluoropolymer is represented by the following formula: It is preferable that the compound has any of the structures represented by the following formula:
  • the fluoropolymer having a nitrogen-containing aromatic ring preferably has any one of these structures.
  • the fluoropolymer having a nitrogen-containing aromatic ring preferably has a carbon atom in the main chain of the fluoropolymer bonded to any one of these structures.
  • the fluoropolymer having a nitrogen-containing aromatic ring preferably has any one of these structures at its terminal, i.e., the carbon atom of the monomer unit at the terminal of the main chain of the fluoropolymer having a nitrogen-containing aromatic ring is preferably bonded to any one of these structures.
  • the fluoropolymer may contain, as a main component, a monomer unit having a fluorinated aliphatic ring.
  • "Containing a monomer unit as a main component” means that the proportion of the monomer unit in question in all monomer units in the fluoropolymer is 50 mol % or more.
  • the proportion of monomer units having a fluorinated aliphatic ring in the fluorinated polymer is preferably at least 80 mol %, more preferably at least 90 mol %, particularly preferably 100 mol %.
  • the fluorine-containing aliphatic ring preferably contains, as ring-constituting atoms, two or more carbon atoms and one, two or three oxygen atoms, and contains no other atoms.
  • the fluorine-containing aliphatic ring preferably does not contain a hydrogen atom.
  • the fluorine-containing aliphatic ring is preferably an aliphatic ring in which all hydrogen atoms are substituted with fluorine atoms.
  • the fluorinated alicyclic ring may be a 4-membered ring, a 5-membered ring, a 6-membered ring, or a 7-membered ring. From the viewpoint of various physical properties of the fluorinated polymer, the fluorinated alicyclic ring is preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 5-membered ring.
  • the fluorine-containing aliphatic 4-membered ring may contain 3 carbon atoms and 1 oxygen atom as ring-constituting atoms.
  • the fluorine-containing aliphatic 6-membered ring may contain, as ring-constituting atoms, 5 carbon atoms and 1 oxygen atom, or 4 carbon atoms and 2 oxygen atoms.
  • Examples of the fluorine-containing aliphatic 6-membered ring include a perfluorotetrahydropyran ring and a perfluoro-1,3-dioxane ring.
  • the fluorine-containing aliphatic 7-membered ring may contain, as ring-constituting atoms, 6 carbon atoms and 1 oxygen atom, 5 carbon atoms and 2 oxygen atoms, or 4 carbon atoms and 3 oxygen atoms.
  • fluorine-containing aliphatic 7-membered ring examples include a perfluorooxepane ring, a perfluoro-1,3-dioxepane ring, a perfluoro-1,4-dioxepane ring, and a perfluoro-1,3,5-trioxepane ring.
  • the fluorine-containing aliphatic ring may have one or more substituents.
  • the substituents may be the same or different.
  • the substituent can be at least one selected from the group consisting of a perfluoroalkyl group (e.g., a linear or branched C1-C5 perfluoroalkyl group) and a perfluoroalkoxy group (e.g., a linear or branched C1-C5 perfluoroalkoxy group).
  • the number of the substituents can be one or more, and can be, for example, 1 to 4, 1 to 3, 1 to 2, 1, 2, 3, or 4.
  • the substituent is preferably at least one group selected from the group consisting of trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, trifluoromethoxy, and perfluoroethoxy, more preferably at least one group selected from the group consisting of trifluoromethyl, perfluoroethyl, perfluoropropyl, and perfluoroisopropyl, and particularly preferably at least one group selected from the group consisting of trifluoromethyl, perfluoroethyl, and trifluoromethoxy.
  • the monomer unit having a fluorinated aliphatic ring may have one or two perfluoroalkylene groups in addition to the fluorinated aliphatic ring.
  • the perfluoroalkylene group can bond to a ring-constituting carbon atom of the fluorinated aliphatic ring to form the main chain of the fluorinated polymer.
  • An example of such a perfluoroalkylene group is represented by the following formula (A1-1):
  • the monomer unit may have one perfluoroalkylene group. When two perfluoroalkylene groups are contained, they may be the same or different .
  • perfluoroalkylene group is an alkylene group represented by the formula: --(CF 2 ) n -- (wherein n is an integer of 1 to 4).
  • the perfluoroalkylene group contained in the monomer unit having a fluorine-containing aliphatic ring may have one or more perfluoroalkyl groups as a substituent. When there are a plurality of such substituents, they may be the same or different.
  • the number of the substituents may be one or more, for example, 1 to 4, 1 to 3, 1 to 2, 1, 2, 3, or 4.
  • the substituent is preferably at least one group selected from the group consisting of trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and heptafluoroisopropyl, and more preferably at least one group selected from the group consisting of trifluoromethyl and pentafluoroethyl.
  • R 1 represents a fluorine atom or a C1-C5 perfluoroalkyl group.
  • R 2 to R 5 each independently represent a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.
  • R 6 to R 9 each independently represent a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.
  • R 1 can be a fluorine atom or a C1- C4 linear or branched perfluoroalkyl group, preferably a fluorine atom, trifluoromethyl, or perfluoroethyl, more preferably a fluorine atom or trifluoromethyl, and particularly preferably a fluorine atom.
  • Preferred examples of the monomer unit (A1) include a monomer unit represented by the following formula (A1-1) (sometimes referred to as “monomer unit (A1-1)" in this specification).
  • R 2 to R 5 each independently represent a fluorine atom, a C1-C3 linear or branched perfluoroalkyl group, or a C1-C3 linear or branched perfluoroalkoxy group.
  • R 2 to R 5 each independently represent preferably a fluorine atom, trifluoromethyl, pentafluoroethyl, or trifluoromethoxy, more preferably a fluorine atom, trifluoromethyl, or trifluoromethoxy.
  • a preferred monomer unit (A2) is a monomer unit represented by formula (A2), in which R2 and R3 each independently represent a fluorine atom, trifluoromethyl, or trifluoromethoxy, and R4 and R5 each independently represent a fluorine atom or trifluoromethyl.
  • Particularly preferred monomer units (A2) are those represented by formula (A2) in which R2 represents a fluorine atom, R3 represents a fluorine atom or trifluoromethoxy, and R4 and R5 are the same and represent a fluorine atom or trifluoromethyl.
  • Preferred examples of the monomer unit (A2) include monomer units represented by the following formulas (which may be referred to as “monomer unit (A2-1)” and “monomer unit (A2-2)" in this specification, respectively).
  • R 6 to R 9 can each independently be a fluorine atom, a C1-C3 linear or branched perfluoroalkyl group, or a C1-C3 linear or branched perfluoroalkoxy group.
  • R 6 to R 9 each independently are preferably a fluorine atom, trifluoromethyl, perfluoroethyl, or trifluoromethoxy, more preferably a fluorine atom, trifluoromethyl, or trifluoromethoxy.
  • a preferred monomer unit (A3) is a monomer unit represented by formula (A3), in which R 6 to R 9 each independently represent a fluorine atom or trifluoromethyl.
  • Preferred examples of the monomer unit (A3) include a monomer unit represented by the following formula (sometimes referred to as “monomer unit (A3-1)" in this specification).
  • the fluoropolymer may contain other monomer units in addition to the monomer units having a fluorinated aliphatic ring contained as the main component.
  • the proportion of the other monomer units in all the monomer units in the fluoropolymer may be 50 mol % or less, preferably 20 mol % or less, more preferably 10 mol % or less, and particularly preferably 0 mol %.
  • R 111 represents a fluorine atom, a C1-C6 perfluoroalkyl group, or a C1-C6 perfluoroalkoxy group.
  • monomer units include, but are not limited to, monomer units represented by the following formula (sometimes referred to as "monomer unit (A11)" in this specification).
  • the fluorine-containing polymer may be a monomer unit (A2-1) and a monomer unit of the following formula (A11-1): (sometimes referred to as "monomer unit (A11-1)" in this specification).
  • R 111 can be a fluorine atom, a linear or branched C1-C6 perfluoroalkyl group, or a linear or branched C1-C6 perfluoroalkoxy group.
  • Preferred R 111 is a fluorine atom, a linear or branched C1-C4 perfluoroalkyl group, or a linear or branched C1-C4 perfluoroalkoxy group. More preferably, R 111 is a fluorine atom, a linear or branched C1-C3 perfluoroalkyl group, or a linear or branched C1-C3 perfluoroalkoxy group. Particularly preferred R 111 is a fluorine atom or trifluoroalkyl.
  • the solvent for the solvent-soluble fluoropolymer is the above-mentioned solvent (C). Therefore, unless otherwise specified, the description of the solvent (C) described below can be applied to this solvent.
  • fluorine-containing polymers soluble in solvents include polyvinyl fluoride [PVF], polyvinylidene fluoride [PVdF], vinylidene fluoride [VdF]/tetrafluoroethylene [TFE] copolymer, VdF/hexafluoropropylene [HFP] copolymer, VdF/TFE/HFP copolymer, VdF/HFP/(meth)acrylic acid copolymer, VdF/chlorotrifluoroethylene [CTFE] copolymer, VdF/pentafluoropropylene copolymer, VdF/perfluoro(alkyl vinyl ether) [PAVE]/TFE copolymer, polyfluorine-containing alkyl allyl
  • Fluorine-containing alkyl allyl ether is a monomer represented by CF 2 ⁇ CFCF 2 -O-Rf (Rf is a perfluoroalkyl group having 1 to 5 carbon atoms).
  • Amorphous perfluoropolymers are perfluoropolymers that contain, as a main component, monomer units having a fluorinated aliphatic ring and have substantially no crystalline structure.
  • the fluoropolymer of the present disclosure may be a fluoropolymer that is soluble in the solvents listed above, in which the polymerization site of the monomer constituting the fluoropolymer is a carbon atom and which has a nitrogen-containing aromatic ring in its structure.
  • the mass average molecular weight of the fluorine-containing polymer can be, for example, in the range of 5,000 to 2,000,000, in the range of 10,000 to 1,800,000, in the range of 10,000 to 1,500,000, in the range of 30,000 to 1,500,000, in the range of 50,000 to 1,350,000, and the like, preferably in the range of 10,000 to 1,800,000, more preferably in the range of 30,000 to 1,500,000, and particularly preferably in the range of 50,000 to 1,350,000.
  • the lower limit of the mass average molecular weight of the fluoropolymer can be, for example, 5000 or more, preferably 10000 or more, more preferably 30000 or more, and particularly preferably 50000 or more.
  • the upper limit of the mass average molecular weight of the fluoropolymer can be, for example, 2000000 or less, preferably 1800000 or less, more preferably 1500000 or less, and particularly preferably 1350000 or less. The lower limit and the upper limit may be appropriately combined.
  • the mass average molecular weight of the fluoropolymer is a value determined by GPC (gel permeation chromatography) method (particularly the GPC method described in the examples).
  • the fluoropolymer can be synthesized by a known method. For example, it can be synthesized by polymerizing monomers corresponding to the structural units of the fluoropolymer.
  • the polymerization method that can be used includes radical polymerization, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc.
  • the method for producing the fluoropolymer the method for producing the fluoropolymer disclosed herein is preferred.
  • the fluoropolymer having a nitrogen-containing aromatic ring can be used in the applications in which the fluoropolymer (A) was used.
  • the fluoropolymer having a nitrogen-containing aromatic ring has high adhesion to metals, and can therefore be used in applications such as sealing resins (e.g., sealing resins for optical elements, sealing resins for semiconductor substrates), adhesives, particularly adhesives for bonding pellicle membranes and frames, and adhesives for bonding fluororesin linings and metal substrates.
  • One embodiment of the present disclosure is a fluororesin adhesive that contains a fluoropolymer having a nitrogen-containing aromatic ring.
  • the fluororesin adhesive may be used to bond a pellicle membrane to a frame, or may be used to bond a fluororesin lining to a metal substrate.
  • One embodiment of the present disclosure is an optical device that includes the sealing resin or the fluororesin adhesive.
  • One embodiment of the present disclosure is a pellicle including a pellicle membrane and a frame, the pellicle containing a fluoropolymer having a nitrogen-containing aromatic ring.
  • the pellicle may be configured such that the pellicle membrane and the frame are bonded together with the fluororesin adhesive.
  • One embodiment of the present disclosure is an exposure processing method in photolithography using a light source with an emission wavelength of 200 nm or less, in which the pellicle is used.
  • the light source with a wavelength of 200 nm or less may be a fluorine gas excimer laser or a fluorine gas excimer laser.
  • the fluoropolymer having a nitrogen-containing aromatic ring can be produced by reacting a fluoropolymer (A) containing, as a main component, a monomer unit having a fluorinated aliphatic ring with a reactive reagent (B) having a nitrogen-containing aromatic ring, in a solvent (C) (preferably an aprotic solvent).
  • Fluorine-containing polymer (A) contains a monomer unit having a fluorinated alicyclic ring as a main component.
  • the fluoropolymer (A) may be the same polymer as the fluoropolymer containing a monomer unit having a fluorinated alicyclic ring as described above as a main component, except that it does not have a nitrogen-containing aromatic ring and a linker. Therefore, various explanations regarding the fluoropolymer containing a monomer unit having a fluorinated alicyclic ring as a main component can be applied to the fluoropolymer (A).
  • the fluoropolymer (A) can be produced by a known method, for example, the method described in WO 2021/085349.
  • the terminal group of the fluoropolymer (A) may be a group corresponding to the polymerization initiator used in the production of the fluoropolymer (A).
  • the terminal group may be, for example, a group represented by the following formula (K): [In the formula, v represents 0 or 1, and R 40 represents an alkyl group or an alkoxy group.]
  • the group (K) is represented by, but is not limited to, these.
  • the terminal group of the fluoropolymer (A) may be -COF.
  • the terminal groups may be the same or different.
  • the alkyl group in R 40 may be a C1-C6 alkyl group, a C1-C5 alkyl group, etc., preferably a C1-C4 alkyl group, more preferably a C1-C3 alkyl group.
  • the alkyl group may be linear or branched.
  • the alkoxy group in R 40 may be a C1-C6 alkoxy group, a C1-C5 alkoxy group, etc., preferably a C1-C4 alkoxy group, more preferably a C1-C3 alkoxy group.
  • the alkoxy group may be linear or branched.
  • the fluoropolymer (A) is heated to convert the terminals to -COF and then hydrolyzed, which results in the by-production of aqueous hydrofluoric acid.
  • the use of water is not essential, and therefore the by-production of aqueous hydrofluoric acid is prevented or reduced.
  • the reactive reagent (B) having a nitrogen-containing aromatic ring may be a nucleophile.
  • the reactive reagent (B) having a nitrogen-containing aromatic ring include 1-(3-aminopropyl)imidazole, 4-(1H-benzimidazol-2-yl)aniline, 2-aminobenzimidazole, 5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, 3-amino-1H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1-aminobenzotriazole, 2-aminobenzotriazole, 1H-1,2,3- Benzotriazole-5-amine, 5-aminobenzotriazole, melamine monomer, 2-methoxy-4
  • the reactive reagent (B) having a nitrogen-containing aromatic ring is represented by the following formula:
  • the compound may be at least one selected from the compounds represented by the following formula:
  • the composition of the present disclosure contains a solvent (C).
  • the solvent (C) is preferably an aprotic solvent.
  • the aprotic solvent may include at least one selected from the group consisting of perfluorosolvents and non-perfluorosolvents.
  • Perfluorosolvents are aprotic solvents that contain fluorine and carbon atoms but do not contain hydrogen atoms. Examples of perfluorosolvents include perfluoroaromatic compounds, perfluorotrialkylamines, perfluoroalkanes, and perfluorocyclic ethers. Perfluorosolvents can be used alone or in combination of two or more.
  • Non-perfluoro solvent is a solvent that contains fluorine atom, carbon atom and hydrogen atom among aprotic solvents.
  • Non-perfluoro solvents include hydrofluorocarbon, hydrofluoroether, and olefin compound that contains at least one chlorine atom.
  • Non-perfluoro solvents can be used alone or in combination of two or more.Non-perfluoro solvents are preferred solvents because they can dissolve the polymer that contains the structural unit (A3) as the main component, which is considered to have low solubility, at a high concentration.
  • the perfluoroaromatic compound may have, for example, one or more perfluoroalkyl groups.
  • the aromatic ring of the perfluoroaromatic compound may be at least one ring selected from the group consisting of a benzene ring, a naphthalene ring, and an anthracene ring.
  • the perfluoroaromatic compound may have one or more aromatic rings (e.g., one, two, three).
  • the perfluoroalkyl group as a substituent is, for example, a linear or branched C1-C6, C1-C5, or C1-C4 perfluoroalkyl group, preferably a linear or branched C1-C3 perfluoroalkyl group, more preferably trifluoromethyl or pentafluoroethyl.
  • the number of the substituents is, for example, 1 to 4, preferably 1 to 3, and more preferably 1 or 2. When there are a plurality of substituents, they may be the same or different.
  • perfluoroaromatic compounds include perfluorobenzene, perfluorotoluene, perfluoroxylene, and perfluoronaphthalene.
  • Preferred examples of the perfluoroaromatic compound include perfluorobenzene and perfluorotoluene.
  • perfluorotrialkylamines include perfluorotrimethylamine, perfluorotriethylamine, perfluorotripropylamine, perfluorotriisopropylamine, perfluorotributylamine, perfluorotrisec-butylamine, perfluorotritert-butylamine, perfluorotripentylamine, perfluorotriisopentylamine, and perfluorotrineopentylamine.
  • Preferred examples of the perfluorotrialkylamine include perfluorotripropylamine and perfluorotributylamine.
  • the perfluoroalkane is, for example, a linear, branched, or cyclic C3-C12 (preferably C3-C10, more preferably C3-C6) perfluoroalkane.
  • perfluoroalkanes include perfluoropentane, perfluoro-2-methylpentane, perfluorohexane, perfluoro-2-methylhexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluorocyclohexane, perfluoro(methylcyclohexane), perfluoro(dimethylcyclohexane) (e.g., perfluoro(1,3-dimethylcyclohexane)), and perfluorodecalin.
  • Preferred examples of perfluoroalkanes include perfluoropentane, perfluorohexane, perfluoroheptane
  • the perfluorocyclic ether is, for example, a perfluorocyclic ether which may have one or more perfluoroalkyl groups.
  • the ring of the perfluorocyclic ether may be a 3- to 6-membered ring.
  • the ring of the perfluorocyclic ether may have one or more oxygen atoms as ring-constituting atoms.
  • the ring preferably has one or two, more preferably one oxygen atom.
  • the perfluoroalkyl group as a substituent is, for example, a linear or branched C1-C6, C1-C5, or C1-C4 perfluoroalkyl group.
  • a preferred perfluoroalkyl group is a linear or branched C1-C3 perfluoroalkyl group.
  • the number of the substituents is, for example, 1 to 4, preferably 1 to 3, and more preferably 1 or 2. When there are a plurality of substituents, they may be the same or different.
  • Examples of perfluoro cyclic ethers include perfluorotetrahydrofuran, perfluoro-5-methyltetrahydrofuran, perfluoro-5-ethyltetrahydrofuran, perfluoro-5-propyltetrahydrofuran, perfluoro-5-butyltetrahydrofuran, and perfluorotetrahydropyran.
  • Preferred examples of the perfluoro cyclic ether include perfluoro-5-ethyltetrahydrofuran and perfluoro-5-butyltetrahydrofuran.
  • Hydrofluoroethers are, for example, fluorine-containing ethers.
  • the global warming potential (GWP) of the hydrofluoroether is preferably not more than 600, more preferably not more than 400, and particularly preferably not more than 300.
  • the lower limit of the global warming potential (GWP) of the hydrofluoroether may be 1 or more, or 5 or more.
  • hydrofluoroethers are CF3CF2CF2CF2OCH3 , CF3CF2CF ( CF3 ) OCH3, CF3CF ( CF3 ) CF2OCH3 , ( CF3 ) 2CFCF2OCH3 , CF3CF2CF2CF2OC2H5 , ( CF3 ) 2CFCF2OC2H5 , CF3CH2OCF2CHF2 , C2F5CF ( OCH3 ) C3F7 , ( CF3 ) 2CHOCH3 , ( CF3 ) 2CFOCH3 .
  • HFE-227me trifluoromethyl 1,2,2,2-tetrafluoroethyl ether
  • HFE-227me difluoromethyl 1,1,2,2,2-pentafluoroethyl ether
  • HFE-227pc trifluoromethyl 1,1,2,2-tetrafluoroethyl ether
  • HFE-245mf difluoromethyl 2,2,2-trifluoroethyl ether
  • HFE-245pf 2,2-difluoroethyl trifluoromethyl ether
  • 1,1,2,3,3-hexafluoropropyl methyl ether CF 3 CHFCF 2 OCH 3
  • 1,1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether 1,1,2,3,3-hexafluoropropyl methyl ether
  • hydrofluoroethers are CF3CF2CF2CF2OCH3 , ( CF3 ) 2CFCF2OCH3 , CF3CF2CF2CF2OC2H5 , ( CF3 ) 2CFCF2OC2H5 , CF3CH2OCF2CHF2 , C2F5CF ( OCH3 ) C3F7 , 1,1,2,3,3 - hexafluoropropyl methyl ether ( CF3CHFCF2OCH3 ) , 1,1,1,2,2 - tetrafluoroethyl 2,2,2 - trifluoroethyl ether ( CHF2CF2OCH2CF3 ) ), and 1,1,1,3,3,3-hexafluoro-2-methoxypropane ((CF 3 ) 2 CHOCH 3 ).
  • the hydrofluoroether may be at least one selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), a compound represented by the following formula (C- 3 ), a compound represented by the following formula (C-4), (CF 3 ) 2 CHOCH 3 , (CF 3 ) 2 CFOCH 3 , CF 3 CHFCF 2 OCH 3 , and CF 3 CHFCF 2 OCF 3 .
  • the hydrofluoroether is represented by the following formula (C-5): R 21 -O-R 22 (C-5) [In the formula, R 21 is linear or branched propyl or butyl in which one or more hydrogen atoms are substituted with fluorine atoms, and R 22 is methyl or ethyl.] More preferred is a compound represented by the formula (C-5): The compound represented by the formula (C-5) may be a compound in which R 21 is perfluorobutyl and R 22 is methyl or ethyl.
  • the olefin compound containing at least one chlorine atom is a C2-C4 (preferably C2-C3) olefin compound containing at least one chlorine atom in its structure, which is a hydrocarbon having 2 to 4 carbon atoms and one or two (preferably one) double bonds, in which at least one hydrogen atom bonded to a carbon atom is substituted with a chlorine atom.
  • the number of chlorine atoms is from 1 to the maximum number that can be substituted, for example, 1, 2, 3, 4, 5, etc.
  • the olefinic compound that contains at least one chlorine atom may also contain at least one (eg, 1, 2, 3, 4, 5, etc.) fluorine atom.
  • the solvent ( C ) is preferably at least one selected from the group consisting of perfluorobenzene , ( CF3 ) 2CFCF2OCH3 , CF3CF2CF2CF2CF2OCH3 , ( CF3 ) 2CFCF2OC2H5 , and CF3CF2CF2CF2CF2OC2H5 .
  • the global warming potential (GWP) of the aprotic solvent can be 600 or less, 400 or less, etc., preferably 375 or less, more preferably 350 or less, and particularly preferably 0.
  • the lower limit of the global warming potential (GWP) of the aprotic solvent may be 1 or more, or 5 or more.
  • the amount of the reactive reagent (B) used in this reaction can be, for example, 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.1 to 100% by mass, 0.1 to 50% by mass, or 0.1 to 20% by mass, relative to the mass of the fluoropolymer (A).
  • the amount of the solvent (C) used in this reaction may be an amount that can function as a solvent based on common technical knowledge, etc. For example, it may be 50% by mass or more, 100% by mass or more, 200% by mass or more, 200 to 5000% by mass, 200 to 3000% by mass, or 200 to 1000% by mass relative to the mass of the fluoropolymer (A).
  • the temperature of this reaction can be, for example, -20 to 120°C, 0 to 100°C, or 5 to 80°C.
  • the time of this reaction can be, for example, 0.01 to 48 hours, 0.1 to 48 hours, or 0.1 to 24 hours.
  • the reaction may be carried out in the presence or absence of an inert gas (e.g., nitrogen gas).
  • an inert gas e.g., nitrogen gas
  • the reaction may be carried out under reduced pressure, atmospheric pressure, or under elevated pressure.
  • the fluoropolymer having a nitrogen-containing aromatic ring produced by this reaction can be isolated or purified, if desired, by conventional methods such as extraction, dissolution, concentration, filtration, precipitation, dehydration, adsorption, chromatography, etc., or a combination of these.
  • composition containing a fluorine-containing polymer having a nitrogen-containing aromatic ring and hydrogen fluoride One embodiment of the present disclosure is a composition containing a fluorine-containing polymer having a nitrogen-containing aromatic ring and hydrogen fluoride.
  • the content of hydrogen fluoride in the composition may be 0.005 ppm to 50 ppm relative to the content of the fluorine-containing polymer having a nitrogen-containing aromatic ring.
  • the composition of the present disclosure is useful as a source of a fluorine-containing polymer having a nitrogen-containing aromatic ring because the hydrogen fluoride content is small and the production cost is reduced by the production method of the present disclosure.
  • the composition of the present disclosure can be produced, for example, by the production method of the present disclosure.
  • the above-mentioned explanation of the fluorine-containing polymer having a nitrogen-containing aromatic ring of the present disclosure can be applied to the fluorine-containing polymer having a nitrogen-containing aromatic ring in the composition of the present disclosure.
  • the content of hydrogen fluoride in the composition may be 0.005 ppm to 50 ppm, or may be 0.005 ppm to 10 ppm, relative to the content of the fluoropolymer having a nitrogen-containing aromatic ring.
  • the composition may further contain other components in addition to the fluoropolymer having a nitrogen-containing aromatic ring and hydrogen fluoride.
  • the amounts of the various components contained in the composition can be adjusted by setting the reaction conditions (e.g., temperature, time, type and amount of raw materials, type and amount of solvent, type and amount of catalyst).
  • the amounts of the various components can be adjusted by purification after production of the fluoropolymer having a nitrogen-containing aromatic ring.
  • Examples of alcohols that are by-produced when the terminal group reacts with the reactive reagent (B) include MeOH, EtOH, n-PrOH, i-PrOH, n-BuOH, s-BuOHt-BuOH, 1-undecanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, and 4-tert-butylcyclohexyl alcohol.
  • the content of those components may be 0.1 ppm to 100 ppm, or 0.1 ppm to 10 ppm, relative to the content of the fluoropolymer having a nitrogen-containing aromatic ring.
  • the molar ratio of tetrafluoroethylene units to perfluoro-n-propoxyethylene units in Polymer 1 is 98:2.
  • n-Pr represents normal propyl
  • Comparative Example 1 1 g of polymer 1 having terminal structure 1 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. When the dissolved state of the polymer was confirmed after one day had passed, a white solid remained and it was not dissolved. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for one day. The obtained polymer was made into a film and IR was measured, and it was confirmed that there was no change in the terminal structure before and after the addition of the reactive reagent.
  • Comparative Example 3 1 g of polymer 2 having terminal structure 2 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. When the dissolved state of the polymer was confirmed after one day had passed, a white solid remained and it was not dissolved. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for one day. The obtained polymer was made into a film and IR was measured, and it was confirmed that there was no change in the terminal structure before and after the addition of the reactive reagent.
  • Comparative Example 4 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of water was added thereto and stirred at 50°C for one day. After one day, the state of dissolution of the polymer was checked and it was found that a white solid remained and it had not dissolved. In addition, the pH was measured with pH test paper and found to be 1-2, so it was determined that hydrofluoric acid water was present. The solvent was distilled off, and the polymer was thoroughly washed with acetone, and then dried at 80°C under reduced pressure for one day. The obtained polymer was made into a film and IR was measured. The peak (1880 cm -1 ) derived from terminal structure 1 disappeared, and new peaks (1809 cm -1 , 1772 cm -1 ) thought to be COOH terminals were confirmed.
  • Example 1 1 g of polymer 2 having terminal structure 1 was added to a glass vial, and 5 g of NMP was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and subjected to IR measurement, and as a result, the peak (1880 cm -1 ) derived from terminal structure 1 disappeared, and peaks (1613 cm -1 , 3341 cm -1 ) thought to be derived from a group newly introduced by reactive reagent 1 were confirmed.
  • the HF content was 0.04 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 2 1 g of polymer 2 having terminal structure 2 was added to a glass vial, and 5 g of NMP was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and the IR was measured, and as a result, the peak (1830 cm -1 ) derived from terminal structure 2 disappeared, and peaks (1613 cm -1 , 3341 cm -1 ) thought to be derived from the group newly introduced by reactive reagent 1 were confirmed.
  • the HF content was 0.08 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 3 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C. The obtained polymer was made into a film and the IR was measured.
  • Example 4 1 g of polymer 3 having terminal structure 2 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. After one day, the solubility was checked and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C. The obtained polymer was made into a film and the IR was measured.
  • Example 5 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 2 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and the IR was measured, and the peak (1882 cm -1 ) derived from terminal structure 1 disappeared, and peaks (1627 cm -1 , 3099 cm -1 ) thought to be derived from the group newly introduced by reactive reagent 2 were confirmed.
  • the HF content was 0.33 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 6 1 g of polymer 3 having terminal structure 2 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 2 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and subjected to IR measurement, and as a result, the peak (1810 cm -1 ) derived from terminal structure 2 disappeared, and peaks (1627 cm -1 , 3099 cm -1 ) thought to be derived from a group newly introduced by reactive reagent 2 were confirmed.
  • the HF content was 0.65 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 7 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 3 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and the IR was measured, and the peak (1882 cm -1 ) derived from terminal structure 1 disappeared, and peaks (1643 cm -1 , 3104 cm -1 ) thought to be derived from the group newly introduced by reactive reagent 3 were confirmed.
  • the HF content was 0.33 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 8 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of PFB was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 4 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day at 80°C under reduced pressure.
  • the obtained polymer was made into a film and the IR was measured, and the peak (1882 cm -1 ) derived from terminal structure 1 disappeared, and a peak (1528 cm -1 ) thought to be derived from a group newly introduced by reactive reagent 4 was confirmed.
  • the HF content was 2.46 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 9 1 g of polymer 3 having terminal structure 1 was added to a glass vial, 5 g of HFE7100 was added thereto, and the mixture was stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 1 was added thereto and the mixture was stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone, and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and subjected to IR measurement, and as a result, the peak (1882 cm -1 ) derived from terminal structure 1 disappeared, and peaks (1681 cm -1 , 3129 cm -1 ) thought to be derived from a group newly introduced by reactive reagent 1 were confirmed.
  • the HF content was 0.16 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 10 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of HFE7100 was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 4 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and the IR was measured, and the peak (1882 cm -1 ) derived from terminal structure 1 disappeared, and a peak (1528 cm -1 ) thought to be derived from a group newly introduced by reactive reagent 4 was confirmed.
  • the HF content was 0.49 ppm.
  • the terminal structure of this polymer is as follows.
  • Example 11 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of HFE7200 was added thereto and stirred for one day. When the state of dissolution of the polymer was confirmed after one day, the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 1 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C. The obtained polymer was made into a film and the IR was measured.
  • Example 12 1 g of polymer 3 having terminal structure 1 was added to a glass vial, and 5 g of HFE7200 was added thereto and stirred for one day. After one day, the state of dissolution of the polymer was confirmed, and the polymer was completely dissolved and was a homogeneous solution. 0.1 g of reactive reagent 4 was added thereto and stirred for one day at 50°C. After stirring, the solvent and reactive reagent were distilled off, and the polymer was thoroughly washed with acetone and then dried for one day under reduced pressure at 80°C.
  • the obtained polymer was made into a film and subjected to IR measurement, and the peak (1882 cm -1 ) derived from terminal structure 1 disappeared, and a peak (1528 cm -1 ) believed to be derived from a group newly introduced by reactive reagent 4 was confirmed.
  • the HF content was 0.04 ppm.
  • the terminal structure of this polymer is as follows.

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Abstract

Le but principal de la présente invention est d'obtenir un polymère contenant du fluor ayant un cycle aromatique contenant de l'azote, son procédé de production, une composition de celui-ci, et analogue.　La présente divulgation concerne, entre autres, un polymère contenant du fluor qui est soluble dans un solvant, un site de polymérisation d'un monomère constituant le polymère contenant du fluor étant un atome de carbone, le polymère ayant un cycle aromatique contenant de l'azote dans sa structure.
PCT/JP2024/024818 2023-07-11 2024-07-09 Polymère contenant du fluor ayant un cycle aromatique contenant de l'azote, son procédé de production et composition associée Pending WO2025013869A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268031A (ja) * 1994-03-31 1995-10-17 Asahi Glass Co Ltd 非晶質含フッ素重合体
JP2003313236A (ja) * 2002-04-23 2003-11-06 Asahi Glass Co Ltd パーハロポリフルオロ重合体の不安定末端基のフッ素化方法
WO2007089017A1 (fr) * 2006-02-03 2007-08-09 Daikin Industries, Ltd. Procede de production de fluoropolymere contenant un groupe –so3h et fluoropolymere contenant un groupe –so3h
JP2008153114A (ja) * 2006-12-19 2008-07-03 Samsung Sdi Co Ltd 燃料電池用固体高分子電解質、燃料電池用固体高分子電解質の製造方法及び燃料電池
WO2011096371A1 (fr) * 2010-02-05 2011-08-11 旭硝子株式会社 Polymère fluoré et composition de résine fluorée durcissable
WO2015046569A1 (fr) * 2013-09-30 2015-04-02 ダイキン工業株式会社 Copolymère contenant du fluor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268031A (ja) * 1994-03-31 1995-10-17 Asahi Glass Co Ltd 非晶質含フッ素重合体
JP2003313236A (ja) * 2002-04-23 2003-11-06 Asahi Glass Co Ltd パーハロポリフルオロ重合体の不安定末端基のフッ素化方法
WO2007089017A1 (fr) * 2006-02-03 2007-08-09 Daikin Industries, Ltd. Procede de production de fluoropolymere contenant un groupe –so3h et fluoropolymere contenant un groupe –so3h
JP2008153114A (ja) * 2006-12-19 2008-07-03 Samsung Sdi Co Ltd 燃料電池用固体高分子電解質、燃料電池用固体高分子電解質の製造方法及び燃料電池
WO2011096371A1 (fr) * 2010-02-05 2011-08-11 旭硝子株式会社 Polymère fluoré et composition de résine fluorée durcissable
WO2015046569A1 (fr) * 2013-09-30 2015-04-02 ダイキン工業株式会社 Copolymère contenant du fluor

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