Fluoropolymer having nitrogen-containing aromatic ring, method for producing same, and composition thereof

Abstract

The main purpose of the present invention is to provide: a fluorine-containing polymer having a nitrogen-containing aromatic ring; a method for producing the fluorine-containing polymer; a composition of the fluorine-containing polymer; and the like. The present invention relates to a fluorine-containing polymer and the like, the fluorine-containing polymer is soluble in a solvent, a polymerization site of a monomer constituting the fluorine-containing polymer is a carbon atom, and the structure of the fluorine-containing polymer has a nitrogen-containing aromatic ring.

Description

TECHNICAL FIELD

[0001] The present application relates to a fluorine-containing polymer having a nitrogen-containing aromatic ring, a production method thereof, and a composition thereof. BACKGROUND

[0002] Fluorine-containing polymers are used in various fields because of their transparency, durability, chemical resistance, stability, and the like. For example, their use as a resin for encapsulating light-emitting elements, an insulating film for an electrowetting device, a protective film constituting a protective member for preventing foreign matter from adhering to a photomask or an intermediate mask in a manufacturing process of a semiconductor device or a liquid crystal display panel, and an adhesive for bonding a frame constituting a protective member and a protective film has been studied (Patent Documents 1 to 8).

[0003] PRIOR ART DOCUMENTS PATENT DOCUMENTS Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2002-188047 Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2004-085639 Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No. 2003-156835 Patent Document 4: Japanese Patent Application Laid-Open (JP-A) No. 2004-039317 Patent Document 5: Japanese Patent Application Laid-Open (JP-A) No. 2007-320072 Patent Document 6: International Publication No. WO 2011 / 027782 Patent Document 7: International Publication No. WO 2013 / 129501 Patent Document 8: International Publication No. WO 2021 / 020565 SUMMARY

[0004] PROBLEMS TO BE SOLVED BY THE INVENTION However, fluorine-containing polymers have low adhesion to metals, and thus their use and the duration of use are sometimes limited. The main object of the present application is to provide a fluorine-containing polymer having a nitrogen-containing aromatic ring, a production method thereof, a composition thereof, and the like.

[0005] In addition, when a functional group is introduced at the end of a fluorine-containing polymer, at present, after the end portion is converted to -COF, the COF is subjected to hydrolysis treatment, but hydrogen fluoride by-product is generated at the time of conversion to -COF or at the time of hydrolysis thereafter, and this hydrogen fluoride dissolves in the water used at the time of hydrolysis, thereby generating a hydrofluoric acid by-product. Since these hydrogen fluoride and hydrofluoric acid are generated in the reaction, in addition to corrosion of the kettle and contamination of the metal, the treatment of the obtained fluorine polymer also becomes difficult, and thus generation of the by-product is undesirable. The main object of the present application is to provide a production method of a fluorine-containing polymer having a functional group end, which suppresses generation of a hydrofluoric acid by-product.

[0006] Technical solution for solving technical problem The present application includes the following modes.

[0007] Item 1. A fluorine-containing polymer, the fluorine-containing polymer being soluble in a solvent, a polymerization site of a monomer constituting the fluorine-containing polymer being a carbon atom, and the fluorine-containing polymer having a nitrogen-containing aromatic ring in its structure.

[0008] Item 2. The fluorine-containing polymer according to item 1, wherein the nitrogen-containing aromatic ring is at least one selected from a nitrogen-containing aromatic ring (1) represented by the following formula (1), a nitrogen-containing aromatic ring (2) represented by the following formula (2), and a nitrogen-containing aromatic ring (3) represented by the following formula (3). [A represents an oxygen atom, a sulfur atom, or a nitrogen atom which can be substituted by 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, X 1 ~ X 4 any one of which represents a carbon atom, and the other X independently represents a nitrogen atom or a carbon atom, at least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when a plurality of carbon atoms are present, is independently bonded to the main chain of the fluorine-containing polymer through a linking group or directly bonded to the main chain of the fluorine-containing polymer, the other carbon atoms constituting the nitrogen-containing aromatic ring, when a plurality of carbon atoms are present, independently can have a substituent, the substituent, when a plurality of substituents are present, independently is a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group, the alkyl group, when a plurality of alkyl groups are present, independently can include a C1-C5 ether bond, and can be substituted by one or more fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, or isocyanate groups. [Y 1 ~ Y 6 any one of which represents a carbon atom, and the other Y independently represents a nitrogen atom or a carbon atom, at least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when a plurality of carbon atoms are present, is independently bonded to the main chain of the fluorine-containing polymer through a linking group or directly bonded to the main chain of the fluorine-containing polymer, the other carbon atoms constituting the nitrogen-containing aromatic ring, when a plurality of carbon atoms are present, independently can have a substituent, the substituent, when a plurality of substituents are present, independently is a fluorine atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, an isocyanate group, or an alkyl group, When multiple alkyl groups are present, they may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. [B represents an oxygen atom, a sulfur atom, or an R that can be substituted.] 20 The substituted nitrogen atom, R 20 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. Z 1 ~Z 8 Any one of the Zs represents a carbon atom, and the other Zs independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. When multiple alkyl groups are present, they may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. Item 3. The fluoropolymer as described in Item 1 or 2, wherein the basic skeleton of the nitrogen-containing aromatic ring is selected from at least one of pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indoleazine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzoisoxazole, thiazole, isothiazole, benzothiazole, benzoisothiazole and purine.

[0009] Item 4. The fluoropolymer as described in Item 1 or 2, wherein the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole and purine.

[0010] Item 5. The fluoropolymer as described in any one of Items 1 to 4, wherein the fluoropolymer is a fluoropolymer comprising a monomer unit having a fluorinated aliphatic ring as a main component, wherein the fluorinated aliphatic ring of the fluoropolymer has one, two or three etherified oxygen atoms as cyclizing atoms, and when the fluorinated aliphatic ring contains multiple such etherified oxygen atoms, the etherified oxygen atoms are not adjacent to each other, and the structure of the fluoropolymer has a nitrogen-containing aromatic ring.

[0011] Item 6. The fluoropolymer as described in Item 5, wherein the monomer unit included as a main component in the fluoropolymer is a monomer unit (A1) shown in formula (A1), a monomer unit (A2) shown in formula (A2), or a monomer unit (A3) shown in formula (A3). [In the formula, R] 1 [This indicates a fluorine atom or a C1-C5 perfluoroalkyl group.] [In the formula, R] 2 ~R 5 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. [In the formula, R] 6 ~R 9 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. Item 7. The fluoropolymer as described in Item 6, wherein the monomer unit included as a main component in the fluoropolymer is the monomer unit (A3) described above.

[0012] Item 8. The fluoropolymer as described in Item 6, wherein the monomer unit included as the main component in the fluoropolymer is a monomer unit (A1-1) shown in the following formula (A1-1), a monomer unit (A2-1) shown in the following formula (A2-1), a monomer unit (A2-2) shown in the following formula (A2-2), or a monomer unit (A3-1) shown in the following formula (A3-1). Item 9. The fluoropolymer as described in Item 8, wherein the monomer unit included as a main component in the fluoropolymer is the monomer unit (A3-1) described above.

[0013] Item 10. The fluoropolymer as described in any one of Items 1 to 5, wherein the monomer unit included as the main component in the fluoropolymer is -(CF2CF2)-, -(CHFCF2)-, -(CH2CF2)-, -(CH2CHF)-, -(CHFCHF)- or -(CF2CClF)-.

[0014] Item 11. The fluoropolymer as described in any one of items 1 to 10, wherein the mass-average molecular weight of the fluoropolymer is in the range of 5,000 to 2,000,000.

[0015] Item 12. The fluoropolymer as described in any one of items 1 to 10, wherein the mass-average molecular weight of the fluoropolymer is in the range of 10,000 to 1,500,000.

[0016] Item 13. The fluoropolymer as described in Item 2, wherein the linker has the structure shown in the following formula (L). [In the formula, v represents 0 or 1, A represents an oxygen atom, a sulfur atom, -O-CH2-, or a nitrogen atom bonded to a hydrogen atom, methyl, ethyl, n-propyl, or isopropyl group, and * represents the side bonded to a nitrogen-containing aromatic ring.] Item 14. The fluoropolymer as described in any one of items 1 to 12, wherein the nitrogen-containing aromatic ring is bonded to one or both of the monomer units at the end of the main chain of the fluoropolymer.

[0017] Item 15. The fluoropolymer as described in Item 2, wherein one of the carbon atoms constituting the nitrogen-containing aromatic ring is bonded to one or both of the monomer units at the end of the main chain of the fluoropolymer via a linking group. The linker and nitrogen-containing aromatic ring bonded to one or two monomer units at the end of the fluoropolymer backbone have any structure as shown in the following formula. The monomer units included as the main components in the above-mentioned fluoropolymers are monomer units shown in the following formula (A3-1): (A3-1), -(CF2CF2)-, -(CHFCF2)-, -(CH2CF2)-, -(CH2CHF)-, -(CHFCHF)-, or -(CF2CClF)-. Item 16. A method for manufacturing a fluoropolymer, wherein the fluoropolymer comprises a monomer unit having a fluorinated aliphatic ring as a main component, and the fluoropolymer has a nitrogen-containing aromatic ring. The above manufacturing method includes a step of reacting a fluoropolymer (A) containing monomer units having fluorinated aliphatic rings as the main component with a reactive reagent (B) having nitrogen-containing aromatic rings in a solvent (C). The aforementioned fluorinated aliphatic ring has one, two, or three ether oxygen atoms as cyclizing atoms. When the fluorinated aliphatic ring contains multiple ether oxygen atoms, the ether oxygen atoms are not adjacent to each other.

[0018] Item 17. The method for manufacturing a fluoropolymer as described in Item 16, wherein the nitrogen-containing aromatic ring is at least one selected from the nitrogen-containing aromatic ring (1) shown in Formula (1), the nitrogen-containing aromatic ring (2) shown in Formula (2) and the nitrogen-containing aromatic ring (3) shown in Formula (3). [A represents an oxygen atom, a sulfur atom, or an R that can be substituted] 10 The substituted nitrogen atom, R 10 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. X 1 ~X 4 In the alphabet, any one of the X's represents a carbon atom, and the other X's independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. When multiple alkyl groups are present, they may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. [Y] 1 ~Y 5 In the first case, any one of the Y atoms represents a carbon atom, and the other Y atoms independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. When multiple alkyl groups are present, they may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. [B represents an oxygen atom, a sulfur atom, or an R that can be substituted.] 20 The substituted nitrogen atom, R 20 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. Z 1 ~Z 8 Any one of the Zs represents a carbon atom, and the other Zs independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. When multiple alkyl groups are present, they may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. Item 18. A method for manufacturing a fluoropolymer as described in Item 16 or 17, wherein the basic skeleton of the nitrogen-containing aromatic ring is selected from at least one of pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indoleazine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzoisoxazole, thiazole, isothiazole, benzothiazole, benzoisothiazole and purine.

[0019] Item 19. A method for manufacturing a fluoropolymer as described in Item 16 or 17, wherein the basic skeleton of the nitrogen-containing aromatic ring is at least one selected from imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole, and purine.

[0020] Item 20. A method for manufacturing a fluoropolymer as described in any one of Items 16 to 19, wherein the reactive reagent (B) is selected from 1-(3-aminopropyl)imidazolium, 4-(1H-benzimidazole-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 (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-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, cyanuric acid monoamide, cyanuric acid diamide, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2-aminopurine, 8-azaadenine, 6-O-methylguanine, 2,6-diaminopurine, N-methoxy-7H-purine-6-amine, 1H-1,2,4-triazol-3-thio The alcohol, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-mercaptobenzimidazole, 2-mercapto-1-methylbenzimidazole, 5-ethoxy-2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-methoxybenzimidazole, trithiocyanate, 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 6-mercaptopurine, 2-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 1H-benzotriazole-1-methanol, 2-aminooxazole, 5-amino-3-methylisooxazole, 3-hydroxy-5-methylisooxazole, muscarinic acid, 3-amino-5-tert-butylisooxazole, 2-aminobenzoxazole and 2-mercaptobenzimidazole, at least one of these.

[0021] Item 21. A method for manufacturing a fluoropolymer as described in any one of Items 16 to 20, wherein the monomer unit included as a main component in the fluoropolymer (A) is a monomer unit (A1) shown in the following formula (A1), a monomer unit (A2) shown in the following formula (A2), or a monomer unit (A3) shown in the following formula (A3). [In the formula, R] 1 [This indicates a fluorine atom or a C1-C5 perfluoroalkyl group.] [In the formula, R] 2 ~R 5 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. [In the formula, R] 6 ~R 9 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. Item 22. A method for manufacturing a fluoropolymer as described in Item 21, wherein the monomer unit included as a main component in the fluoropolymer (A) is the monomer unit (A3).

[0022] Item 23. A method for manufacturing a fluoropolymer as described in Item 21, wherein the monomer unit included as a main component in the fluoropolymer (A) is a monomer unit (A1-1) shown in the following formula (A1-1), a monomer unit (A2-1) shown in the following formula (A2-1), a monomer unit (A2-2) shown in the following formula (A2-2), or a monomer unit (A3-1) shown in the following formula (A3-1). Item 24. A method for manufacturing a fluoropolymer as described in Item 23, wherein the monomer unit included as a main component in the fluoropolymer (A) is the monomer unit (A3-1) described above.

[0023] Item 25. A method for manufacturing a fluoropolymer as described in any one of items 16 to 24, wherein the solvent (C) is an aprotic solvent.

[0024] Item 26. The method for manufacturing a fluoropolymer as described in Item 25, wherein the aprotic solvent is at least one solvent selected from perfluoroaromatic compounds, perfluorotrialkylamines, perfluoroalkanes, hydrofluorocarbons, perfluorocyclic ethers, hydrofluoroethers, and olefin compounds containing at least one chlorine atom.

[0025] Item 27. The method for manufacturing a fluoropolymer as described in Item 25, wherein the aprotic solvent is a hydrofluoroether.

[0026] Item 28. A method for manufacturing a fluoropolymer as described in Item 25, wherein the global warming potential (GWP) of the aforementioned aprotic solvent is 400 or less.

[0027] Item 29. A method for manufacturing a fluoropolymer as described in Item 25, wherein the aprotic solvent is at least one hydrofluoroether selected from the compounds shown in formula (C-1), formula (C-2), formula (C-3), formula (C-4), (CF3)2CHOCH3, (CF3)2CFOCH3, CF3CHFCF2OCH3, and CF3CHFCF2OCF3.

[0028] F(CF2) p O(CH2) q H (C-1) [In the formula, p is an integer from 1 to 6, and q is an integer from 1 to 4.] H(CF2) p O(CF2) q F (C-2) [In the formula, p and q have the same meanings as described above.] H(CF2) p O(CH2) q H (C-3) [In the formula, p and q have the same meanings as described above.] X (CF2) p CH2O(CF2) q H (C-4) [In the formula, X represents a fluorine atom or a hydrogen atom, and the meanings of p and q are the same as above.] Item 30. The method for manufacturing a fluoropolymer as described in Item 25, wherein the aprotic solvent is a compound represented by formula (C-5).

[0029] R 21 -O-R 22 (C-5) [In the formula, R] 21 R is a straight-chain or branched propyl or butyl group in which one or more hydrogen atoms are replaced by fluorine atoms. 22 It is either methyl or ethyl. Item 31. A method for manufacturing a fluoropolymer as described in any one of items 16 to 30, wherein the mass-average molecular weight of the fluoropolymer is in the range of 5,000 to 2,000,000.

[0030] Item 32. A method for manufacturing a fluoropolymer as described in any one of items 16 to 30, wherein the mass-average molecular weight of the fluoropolymer is in the range of 10,000 to 1,500,000.

[0031] Item 33. A method for manufacturing a fluoropolymer as described in any one of items 16 to 32, wherein the fluoropolymer (A) has at least one group selected from COF groups and groups (K) represented by the following formula (K). [In the formula, v represents 0 or 1, R] 40 Indicates alkyl or alkoxy. Item 34. A method for manufacturing a fluoropolymer as described in Item 33, wherein one or two of the monomer units at the ends of the main chain of the fluoropolymer (A) have at least one group selected from the COF group and the group (K).

[0032] Item 35. A method for manufacturing a fluoropolymer as described in Item 17, wherein, in a fluoropolymer comprising a monomer unit having the aforementioned 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 to one or two monomer units at the end of the main chain of the fluoropolymer via a linking group. The linker and nitrogen-containing aromatic ring bonded to one or two monomer units at the end of the main chain of the fluoropolymer have any structure as shown in the following formula. The reactive reagent (B) described above can be any compound represented by the following formula. The monomer unit included as the main component in the above-mentioned fluoropolymer (A) is the monomer unit (A3-1) shown in the following formula (A3-1). The terminal structure of the above-mentioned fluoropolymer (A) is -COF or -CF2-O-CO-O-n-propyl. The solvent (C) mentioned above is selected from at least one of perfluorobenzene, (CF3)2CFCF2OCH3, CF3CF2CF2CF2OCH3, (CF3)2CFCF2OC2H5 and CF3CF2CF2CF2OC2H5.

[0033] Item 36. An encapsulating resin comprising any one of items 1 to 15 containing a fluoropolymer.

[0034] Item 37. A fluoropolymer adhesive comprising any one of items 1 to 15.

[0035] Item 38. The fluoropolymer adhesive as described in Item 37, used for bonding protective films and frames.

[0036] Item 39. An optical device comprising any one of the encapsulating resin described in Item 36, the fluoropolymer adhesive described in Item 37, and the fluoropolymer adhesive described in Item 38.

[0037] Item 40. A protective element comprising a protective film and a frame, wherein the protective element contains any one of items 1 to 15 containing a fluoropolymer.

[0038] Item 41. The protective element as described in Item 40, wherein the protective film and the frame are bonded by the fluoropolymer adhesive described in Item 37.

[0039] Item 42. An exposure processing method, which is an exposure processing method in photolithography using a light source with an emission wavelength of less than 200 nm, using the protective element described in Item 40.

[0040] Item 43. The exposure processing method as described in Item 42, wherein the light source with a wavelength below 200 nm is a fluorine excimer laser or a fluorine excimer laser.

[0041] Item 44. A composition comprising the fluoropolymer and hydrogen fluoride as described in any one of items 1 to 15. The content of hydrogen fluoride is 0.005 ppm to 50 ppm relative to the content of the fluoropolymer.

[0042] Item 45. The composition as described in Item 44, wherein the content of the hydrogen fluoride is 0.005 ppm to 10 ppm relative to the content of the fluoropolymer.

[0043] Invention Effects This invention provides a fluoropolymer with improved adhesion to metals. It also provides a method for manufacturing a fluoropolymer that suppresses the formation of hydrogen fluoride byproducts. Furthermore, it provides a composition containing a fluoropolymer that has low hydrogen fluoride content and is useful as a source of supply for fluoropolymers. Detailed Implementation

[0044] The above summary of the present invention is not intended to describe all or all of the embodiments disclosed herein.

[0045] The following description of the present invention illustrates embodiments in more detail.

[0046] Guidance is provided by way of illustration in some parts of the invention, and such illustrations can be used in various combinations.

[0047] In various situations, the illustrated group can serve as a non-exclusive and representative group.

[0048] All publications, patents, and patent applications referenced in this specification may be directly incorporated herein by reference.

[0049] the term Unless otherwise specified, the symbols and abbreviations in this specification shall be understood, in the context of this specification, to have the meaning commonly used in the technical field to which this invention pertains.

[0050] In this specification, the use of the word "contains" is intended to include both the expression "substantially constitutes" and the expression "consisting of".

[0051] Unless otherwise specified, the procedures, treatments, or operations described in this instruction manual may be performed at room temperature. In this instruction manual, room temperature may refer to a temperature in the range of 10–40°C.

[0052] In this specification, the designation “Cn-Cm” (where n and m are numbers) indicates, as commonly understood by those skilled in the art, a number of carbon atoms greater than n and less than m.

[0053] In this specification, unless otherwise specified by those skilled in the art, the labeling of compounds may include all stereoisomers (enantiomers, diastereomers, geometric isomers, etc.).

[0054] In this specification, unless otherwise specified, a "fluorinated aliphatic ring" has multiple carbon atoms and one, two, or three ether-type oxygen atoms as cyclizing atoms. When a "fluorinated aliphatic ring" contains multiple oxygen atoms as cyclizing atoms, these oxygen atoms are not adjacent to each other.

[0055] "Fluoro-containing aliphatic rings" include saturated aliphatic monocycles containing fluorine atoms.

[0056] "Fluoro-containing aliphatic rings" include rings with 4 or more members (e.g., 4-membered rings, 5-membered rings, 6-membered rings, 7-membered rings).

[0057] The "fluorinated aliphatic ring" may have at least one substituent selected from perfluoroalkyl (e.g., C1-C5 straight-chain or branched perfluoroalkyl) and perfluoroalkoxy (e.g., C1-C5 straight-chain or branched perfluoroalkoxy). When there is more than one substituent, for example, there may be 1 to 4, 1 to 3, 1 to 2, 1, 2, 3, or 4 substituents.

[0058] In a "fluorinated aliphatic ring", the cyclic carbon atom can have either or both of a fluorine atom and a substituent.

[0059] Examples of “fluorinated aliphatic rings” include perfluorooxetanes that may have one or more substituents, perfluorotetrahydrofurans that may have one or more substituents, perfluorodioxetanes that may have one or more substituents, perfluorotetrahydropyrans that may have one or more substituents, perfluoro-1,3-dioxanes that may have one or more substituents, perfluorooxetanes that may have one or more substituents, perfluoro-1,3-dioxetanes that may have one or more substituents, perfluoro-1,4-dioxetanes that may have one or more substituents, and perfluoro-1,3,5-trioxetanes that may have one or more substituents.

[0060] In this specification, unless otherwise specified, examples of "alkyl" include straight-chain or branched C1-C10 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Alkyl groups can be C1-C6, C1-C5, C1-C4, or C1-C3 alkyl groups.

[0061] In this specification, alkyl groups may or may not contain C1-C5 ether bonds. Alkyl groups containing C1-C5 ether bonds may be alkyl groups containing C1-C4 ether bonds, alkyl groups containing C1-C3 ether bonds, alkyl groups containing C2-C5 ether bonds, or alkyl groups containing C3-C5 ether bonds. Examples of alkyl groups containing C1-C5 ether bonds include CH3OCH2-, CH3CH2OCH2-, CH3OCH2CH2-, CH3CH2CH2OCH2-, CH3CH2OCH2CH2-, CH3OCH2CH2CH2-, CH3CH2CH2CH2OCH2-, CH3CH2CH2O CH2CH2-, CH3CH2OCH2CH2CH2-, CH3OCH2CH2CH2CH2-, CH3OCH(CH3)-, CH3CH(CH3)OCH2-, CH3CH2OCH(CH3)-, CH3OC(CH3)2- and CH3OCH2CH2OCH2-.

[0062] In this specification, unless otherwise specified, "fluoroalkyl" means an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. "Fluoroalkyl" can be linear or branched.

[0063] The number of carbon atoms in a "fluoroalkyl" group can be, for example, 1–12, 1–6, 1–5, 1–4, 1–3, 6, 5, 4, 3, 2, or 1.

[0064] The number of fluorine atoms in a "fluoroalkyl" group can be more than one (e.g., 1 to 3, 1 to 5, 1 to 9, 1 to 11, 1 to the maximum number that can be substituted).

[0065] "Fluoroalkyl" includes perfluoroalkyl.

[0066] "Perfluoroalkyl" is a group in which all hydrogen atoms in an alkyl group are replaced by fluorine atoms.

[0067] Examples of perfluoroalkyl groups include trifluoromethyl (CF3-), pentafluoroethyl (C2F5-), heptafluoropropyl (CF3CF2CF2-), and heptafluoroisopropyl ((CF3)2CF-).

[0068] As "fluoroalkyl", examples include monofluoromethyl, difluoromethyl, trifluoromethyl (CF3-), 2,2,2-trifluoroethyl (CF3CH2-), perfluoroethyl (C2F5-), tetrafluoropropyl (e.g., HCF2CF2CH2-), hexafluoropropyl (e.g., (CF3)2CH-), perfluorobutyl (e.g., CF3CF2CF2CF2-), octafluoropentyl (e.g., HCF2CF2CF2CF2CH2-), perfluoropentyl (e.g., CF3CF2CF2CF2CF2-), and perfluorohexyl (e.g., CF3CF2CF2CF2CF2CF2-).

[0069] In this specification, unless otherwise specified, "alkoxy" can be a group represented by RO- [where R is an alkyl group (e.g., C1-C10 alkyl)].

[0070] Examples of "alkoxy" include straight-chain or branched C1-C10 alkoxy compounds such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy.

[0071] In this specification, unless otherwise specified, "fluoroalkoxy" refers to an alkoxy group in which at least one hydrogen atom is replaced by a fluorine atom. "Fluoroalkoxy" can be linear or branched.

[0072] The number of carbon atoms in a "fluoroalkoxy group" can be, for example, 1–12, 1–6, 1–5, 1–4, 1–3, 6, 5, 4, 3, 2, or 1.

[0073] The number of fluorine atoms in a "fluoroalkoxy" can be more than one (e.g., 1 to 3, 1 to 5, 1 to 9, 1 to 11, up to the maximum number that can be substituted).

[0074] "Fluoroalkoxy" includes perfluoroalkoxy.

[0075] "Perfluoroalkoxy" is a group in which all hydrogen atoms in an alkoxy group are replaced by fluorine atoms.

[0076] Examples of perfluoroalkoxy groups include trifluoromethoxy (CF3O-), pentafluoroethoxy (C2F5O-), heptafluoropropoxy (CF3CF2CF2O-), and heptafluoroisopropoxy ((CF3)2CFO-).

[0077] As "fluoroalkoxy", specifically, examples include monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy (CF3CH2O-), perfluoroethoxy (C2F5O-), tetrafluoropropoxy (e.g., HCF2CF2CH2O-), hexafluoropropoxy (e.g., (CF3)2CHO-), perfluorobutoxy (e.g., CF3CF2CF2CF2O-), octafluoropentoxy (e.g., HCF2CF2CF2CF2CH2O-), perfluoropentoxy (e.g., CF3CF2CF2CF2CF2O-), and perfluorohexyloxy (e.g., CF3CF2CF2CF2CF2CF2O-).

[0078] In this specification, unless otherwise specified, a "nitrogen-containing aromatic ring" has at least one nitrogen atom and at least one carbon atom as ring-forming atoms. The number of nitrogen atoms constituting the ring can be, for example, 1, 2, 3, 4, 5, 6, etc., but not greater than the number of ring-forming atoms minus 1.

[0079] The cyclic atoms other than the nitrogen atom can be all carbon atoms, or at least one carbon atom and other atoms. The number of cyclic carbon atoms can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, etc., but not greater than the number of cyclic atoms minus 1. When at least one (preferably 1 or 2, more preferably 1) cyclic carbon atom is present in multiple forms, it is preferably independently bonded to the main chain of the fluoropolymer via a linker, or directly bonded to the main chain of the fluoropolymer.

[0080] Other cyclic atoms can be oxygen atoms, sulfur atoms, etc., with oxygen atoms or sulfur atoms being preferred. The number of other cyclic atoms can be, for example, 1 or 2, with 1 being preferred.

[0081] Cyclic atoms can also have substituents. Substituents can be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, alkyl groups, etc. The number of substituents can be, for example, 1, 2, 3, 4, etc. When multiple substituents are present, they can be the same or different. Examples of substituents include fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, alkyl groups, etc.

[0082] The nitrogen-containing aromatic ring may also contain oxygen or sulfur atoms as other cyclic atoms. The number of other cyclic atoms can be 1, 2, etc., with 1 being preferred.

[0083] "Nitrogen-containing aromatic rings" include monocyclic aromatic rings containing at least one nitrogen atom. "Nitrogen-containing aromatic rings" include rings with four or more members (e.g., 4-membered, 5-membered, 6-membered, and 7-membered rings). Examples of basic ring structures for "nitrogen-containing aromatic rings" include pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrazine, triazine, indole, isoindole, indoleazine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benziisoxazole, thiazole, isothiazole, benzothiazole, benziisothiazole, purine, etc., with imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole, purine, etc., being preferred. As mentioned above, these rings are preferably bonded to the backbone of a fluoropolymer via cyclizing carbon atoms. As mentioned above, the cyclizing atoms of these rings may also have substituents.

[0084] Fluoropolymers with nitrogen-containing aromatic rings One embodiment of the present invention is a fluoropolymer having a nitrogen-containing aromatic ring. The fluoropolymer is soluble in a solvent (preferably an aprotic solvent). In the fluoropolymer, the polymerization site of the monomer constituting the polymer is a carbon atom. The polymerization site of the monomer constituting the fluoropolymer is the site formed by the combination of the monomer with other monomers during polymerization. Typically, it is the site where monomer units are combined with monomer units.

[0085] Fluoropolymers contain nitrogen-containing aromatic rings in their structure. When a fluoropolymer has multiple nitrogen-containing aromatic rings, these rings can be identical or different. The nitrogen-containing aromatic rings can be contained in the main chain or in the side chain of the fluoropolymer. The fluoropolymer of this invention exhibits high adhesion to metals due to the presence of nitrogen-containing aromatic rings in its structure.

[0086] The cyclic carbon atom of the nitrogen-containing aromatic ring is preferably bonded to the main chain of the fluoropolymer via a linker group, or directly bonded to the main chain of the fluoropolymer, more preferably via a linker group. The nitrogen-containing aromatic ring can be bonded to the terminal monomer units of the fluoropolymer main chain, or to monomer units not at the terminal of the main chain. The nitrogen-containing aromatic ring can also be bonded to one or two of the terminal monomer units of the fluoropolymer main chain.

[0087] The connecting base can be, for example, the structure shown in the following formula (L). [In the formula, v represents 0 or 1, A represents an oxygen atom, a sulfur atom, -O-CH2-, or a nitrogen atom bonded to a hydrogen atom, methyl, ethyl, n-propyl, or isopropyl group, and * represents the side bonded to a nitrogen-containing aromatic ring.] A can be an oxygen atom, a sulfur atom, -O-CH2-, or a nitrogen atom bonded to a hydrogen atom.

[0088] The linker can be -CO-NH-*, -CF2-O-CO-NH-*, or -CO-S-* [in these chemical structures, * indicates the side bonded to the nitrogen-containing aromatic ring].

[0089] Examples of ring structures that form the basis of nitrogen-containing aromatic rings include pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indoleazine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzoisoxazole, thiazole, isothiazole, benzothiazole, benzoisothiazole, and purine. Pyrazole, imidazole, triazole, oxazole, isoxazole, pyridazine, pyrimidine, triazine, benzimidazole, benzotriazole, benzothiazole, and purine are preferred. Imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole, and purine are even more preferred.

[0090] The nitrogen-containing aromatic ring may be, for example, at least one selected from the nitrogen-containing aromatic ring (1) shown in formula (1), the nitrogen-containing aromatic ring (2) shown in formula (2) and the nitrogen-containing aromatic ring (3) shown in formula (3). [A represents an oxygen atom, a sulfur atom, or an R that can be substituted] 10 The substituted nitrogen atom, R 10 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group, X 1 ~X 4 Any one of the X's represents a carbon atom, and the other X's independently represent a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple X's are present, is independently bonded to the backbone of the fluoropolymer via a linking group or directly bonded to the backbone of the fluoropolymer. Other carbon atoms constituting the nitrogen-containing aromatic ring, when multiple X's are present, can independently have substituents. When multiple substituents are present, these substituents can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. When multiple alkyl groups are present, they can independently contain C1-C5 ether bonds and can be substituted by one or more fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, or isocyanate groups. [Y] 1 ~Y 6Any one of the Y atoms represents a carbon atom, and the others independently represent a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluoropolymer via a linking group or directly bonded to the backbone of the fluoropolymer. Other carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, can independently have substituents, which, when multiple are present, are independently fluorine, hydroxyl, mercapto, amino, cyano, isocyanate, or alkyl groups. When multiple alkyl groups are present, they can independently contain C1-C5 ether bonds and can be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. [B represents an oxygen atom, a sulfur atom, or an R that can be substituted.] 20 The substituted nitrogen atom, R 20 Z represents a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. 1 ~Z 8 Any one of the Zs represents a carbon atom, and the others independently represent a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple Zs are present, is independently bonded to the backbone of the fluoropolymer via a linking group or directly bonded to the backbone of the fluoropolymer. Other carbon atoms constituting the nitrogen-containing aromatic ring, when multiple Zs are present, can independently have substituents. When multiple substituents are present, these substituents are independently fluorine, hydroxyl, mercapto, amino, cyano, isocyanate, or alkyl groups. When multiple alkyl groups are present, they can independently contain C1-C5 ether bonds and can be substituted by one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. In nitrogen-containing aromatic rings (1), A and X 1 ~X 4 At least one of them is a nitrogen atom. In A and X 1 ~X 4 In this context, the number of nitrogen atoms can be 1, 2, or 3. In A and X... 1 ~X 4 In this context, the number of carbon atoms can be 2, 3, or 4. (A and X) 1 ~X 4 It is preferably composed of nitrogen atoms and carbon atoms.

[0091] As the basic ring structure of nitrogen-containing aromatic rings (1), examples include pyrrole, pyrazole, imidazole, triazole, oxazole, isoxazole, thiazole, isothiazole, etc.

[0092] In nitrogen-containing aromatic rings (2), Y 1 ~Y 6 At least one of them is a nitrogen atom. In Y 1~Y 6 In Y, the number of nitrogen atoms can be 1, 2, or 3. 1 ~Y 6 In Y, the number of carbon atoms can be 3, 4, or 5. 1 ~Y 6 It is preferably composed of nitrogen atoms and carbon atoms.

[0093] As the basic ring structure of nitrogen-containing aromatic rings (2), for example, pyridine, pyridazine, pyrimidine, pyrazine, triazine, etc. can be listed.

[0094] In nitrogen-containing aromatic rings (3), B and Z 1 ~Z 8 At least one of them is a nitrogen atom. B, Z 1 and Z 2 At least one of them is a nitrogen atom, preferably Z. 3 ~Z 8 They are all carbon atoms. In Z... 1 ~Z 8 In Z, the number of nitrogen atoms can be 1, 2, or 3. 1 ~Z 8 In B and Z, the number of carbon atoms can be 5, 6, or 7. 1 ~Z 8 It is preferably composed of nitrogen atoms and carbon atoms.

[0095] As the basic ring structure of nitrogen-containing aromatic rings (3), examples include indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzoisoxazole, benzothiazole, benzoisothiazole, purine, etc.

[0096] In nitrogen-containing aromatic rings (1), R 10 It can be a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group, and can be hydroxyl, mercapto, or alkyl. R 10 When it is an alkyl group, it can contain C1-C5 ether bonds, for example, it can be CH3OCH2-, CH3CH2OCH2-, CH3OCH2CH2-, CH3CH2CH2OCH2-, CH3OCH2CH2CH2-, CH3CH2CH2CH2OCH2-, CH3CH2CH2OCH2CH2-, CH3CH2OCH2CH2CH2-, CH3OCH2CH2CH2CH2-, CH3OCH(CH3)-, CH3CH(CH3)OCH2-, CH3CH2OCH(CH3)-, CH3OC(CH3)2- and CH3OCH2CH2OCH2-.

[0097] In nitrogen-containing aromatic rings (3), R 20 It can be a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group, and can be hydroxyl, mercapto, or alkyl. R 20 When it is an alkyl group, it can contain C1-C5 ether bonds, for example, it can be CH3OCH2-, CH3CH2OCH2-, CH3OCH2CH2-, CH3CH2CH2OCH2-, CH3OCH2CH2CH2-, CH3CH2CH2CH2OCH2-, CH3CH2CH2OCH2CH2-, CH3CH2OCH2CH2CH2-, CH3OCH2CH2CH2CH2-, CH3OCH(CH3)-, CH3CH(CH3)OCH2-, CH3CH2OCH(CH3)-, CH3OC(CH3)2- and CH3OCH2CH2OCH2-.

[0098] In the nitrogen-containing aromatic rings (1) to (3), the cyclic carbon atom may have substituents. Substituents may be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, alkyl groups, etc., and may be hydroxyl groups, mercapto groups, cyano groups, or alkyl groups, etc. When the substituent is an alkyl group, it can contain C1-C5 ether bonds, for example, CH3OCH2-, CH3CH2OCH2-, CH3OCH2CH2-, CH3CH2CH2OCH2-, CH3OCH2CH2CH2-, CH3CH2CH2CH2OCH2-, CH3CH2CH2OCH2CH2-, CH3CH2OCH2CH2CH2-, CH3OCH2CH2CH2CH2-, CH3OCH(CH3)-, CH3CH(CH3)OCH2-, CH3CH2OCH(CH3)-, CH3OC(CH3)2-, and CH3OCH2CH2OCH2-. Multiple substituents can be the same or different.

[0099] In a nitrogen-containing aromatic ring (1), the number of substituents of the cyclic carbon atom can be 0 to 3, 0 to 2, 0 or 1, or 0.

[0100] In a nitrogen-containing aromatic ring (2), the number of substituents of the cyclic carbon atom can be 0 to 4, 0 to 3, 0 to 2, 0 or 1, or 0.

[0101] In a nitrogen-containing aromatic ring (3), the number of substituents of the cyclic carbon atom can be 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 or 1, or 0.

[0102] 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 monomer units at the end of the main chain of the fluoropolymer via a linker. The structure of the linker bonded to one or two monomer units at the end of the main chain of the fluoropolymer and the nitrogen-containing aromatic ring is preferably any structure shown in the following formula. Fluoropolymers having nitrogen-containing aromatic rings preferably have any of these structures. That is, fluoropolymers having nitrogen-containing aromatic rings preferably have carbon atoms in the main chain of the fluoropolymer bonded to any of these structures.

[0103] Fluoropolymers having nitrogen-containing aromatic rings preferably have any of these structures at their ends. That is, the carbon atoms of the monomer units at the ends of the main chain of the fluoropolymer having nitrogen-containing aromatic rings are preferably bonded to any of these structures.

[0104] Fluoropolymers contain monomer units with fluorinated aliphatic rings as the main component. "Containing monomer units as the main component" means that the monomer unit accounts for more than 50 mol% of all monomer units in the fluoropolymer.

[0105] The proportion of monomer units having fluorinated aliphatic rings in the fluoropolymer is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.

[0106] The fluoropolymer may contain one or more monomer units with fluorinated aliphatic rings, preferably one to three, more preferably one or two, and particularly preferably one.

[0107] In a monomer unit having a fluorinated aliphatic ring, as a cyclic atom, there are 1, 2 or 3 etherified oxygen atoms. When the fluorinated aliphatic ring contains multiple etherified oxygen atoms, the etherified oxygen atoms are not adjacent to each other.

[0108] In a fluorinated aliphatic ring, as a cyclic atom, there are two or more (e.g., 2, 3, or 4) carbon atoms, and it may contain one or more (e.g., 1, 2, 3, 4, 5, or 6) carbon-carbon bonds formed between adjacent carbon atoms.

[0109] In a fluorinated aliphatic ring, the ring-forming atoms contain two or more carbon atoms and one, two or three oxygen atoms, and preferably no other atoms.

[0110] Fluorinated aliphatic rings are preferably free of hydrogen atoms.

[0111] The preferred aliphatic ring containing fluorine is one in which all hydrogen atoms are replaced by fluorine atoms.

[0112] The fluorinated aliphatic ring can 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 fluorinated polymers, the fluorinated aliphatic ring is preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 5-membered ring.

[0113] In fluorinated aliphatic four-membered rings, the cyclic atoms can consist of three carbon atoms and one oxygen atom. Examples of fluorinated aliphatic four-membered rings include perfluorooxocyclic butane rings.

[0114] In fluorinated aliphatic 5-membered rings, the cyclic atoms can contain 4 carbon atoms and 1 oxygen atom, or they can contain 3 carbon atoms and 2 oxygen atoms. Examples of fluorinated aliphatic 5-membered rings include the perfluorotetrahydrofuran ring and the perfluorodioxane ring.

[0115] In a fluorinated aliphatic 6-membered ring, the cyclizing atoms can contain 5 carbon atoms and 1 oxygen atom, or they can contain 4 carbon atoms and 2 oxygen atoms. Examples of fluorinated aliphatic 6-membered rings include the perfluorotetrahydropyran ring and the perfluoro-1,3-dioxane ring.

[0116] In fluorinated aliphatic 7-membered rings, the cyclizing atoms can contain 6 carbon atoms and 1 oxygen atom, 5 carbon atoms and 2 oxygen atoms, or 4 carbon atoms and 3 oxygen atoms. Examples of fluorinated aliphatic 7-membered rings include perfluorooxetine heptane rings, perfluoro-1,3-dioxetine heptane rings, perfluoro-1,4-dioxetine heptane rings, and perfluoro-1,3,5-trioxetine heptane rings.

[0117] Fluorinated aliphatic rings can have more than one substituent. When multiple substituents are present, they can be the same or different.

[0118] The substituents may be selected from at least one of perfluoroalkyl (e.g., straight-chain or branched C1-C5 perfluoroalkyl) and perfluoroalkoxy (e.g., straight-chain or branched C1-C5 perfluoroalkoxy). The number of substituents may be one or more, for example, 1 to 4, 1 to 3, 1 to 2, 1, 2, 3 or 4.

[0119] As a substituent, it is preferably selected from at least one group selected from trifluoromethyl, perfluoroethyl, perfluoron-propyl, perfluoroisopropyl, trifluoromethoxy and perfluoroethoxy, more preferably selected from at least one group selected from trifluoromethyl, perfluoroethyl, perfluoron-propyl and perfluoroisopropyl, and particularly preferably selected from at least one group selected from trifluoromethyl, perfluoroethyl and trifluoromethoxy.

[0120] In addition to the fluorinated aliphatic ring, the monomer unit with the fluorinated aliphatic ring may also have one or two additional perfluoroalkyl groups. These perfluoroalkyl groups can bond to the cyclic carbon atoms of the fluorinated aliphatic ring to form the backbone of the fluorinated polymer.

[0121] An example of such a perfluoroalkylene group is two -CF2- groups in the monomer unit shown in formula (A1-1), excluding the perfluoromethylene group forming the ring. The monomer unit may also contain only one perfluoroalkylene group. In the case of two perfluoroalkylene groups, they may be the same or different. An example of a perfluoroalkylene group is the alkylene group represented by -(CF2)n- [where n represents an integer from 1 to 4].

[0122] The perfluoroalkylene group contained in the monomer unit having a fluorinated aliphatic ring may have one or more perfluoroalkyl groups as substituents. These substituents may be the same or different when multiple substituents are present. For example, when there are one or more substituents, they may be 1 to 4, 1 to 3, 1 to 2, 1, 2, 3, or 4.

[0123] As a substituent, it is preferably selected from at least one group selected from trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl and heptafluoroisopropyl, and more preferably selected from at least one group selected from trifluoromethyl and pentafluoroethyl.

[0124] The monomer unit having a fluorinated aliphatic ring can be any of the monomer units shown in formulas (A1) to (A3) below (sometimes referred to in this specification as "monomer unit (A1)", "monomer unit (A2)" and "monomer unit (A3)" respectively). Monomer units (A1), (A2) and (A3) can be a single type or a combination of two or more types. [In the formula, R] 1 [This indicates a fluorine atom or a C1-C5 perfluoroalkyl group.] [In the formula, R] 2 ~R 5 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. [In the formula, R] 6 ~R 9 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. In the single-unit cell (A1), R 1 It can be a fluorine atom, or a C1-C4 straight-chain or branched perfluoroalkyl group. R 1 The preferred components are fluorine atoms, trifluoromethyl or perfluoroethyl, more preferably fluorine atoms or trifluoromethyl, and particularly preferably fluorine atoms.

[0125] A preferred example of a single-unit (A1) includes the single-unit shown in the following formula (A1-1) (sometimes referred to as "single-unit (A1-1)" in this specification). In the single-unit cell (A2), R 2 ~R 5 Each can be independent and can be a fluorine atom, a C1-C3 straight-chain or branched perfluoroalkyl group, or a C1-C3 straight-chain or branched perfluoroalkoxy group. R 2 ~R 5 Fluorine atoms, trifluoromethyl, pentafluoroethyl or trifluoromethoxy are preferred, and fluorine atoms, trifluoromethyl or trifluoromethoxy are more preferred.

[0126] The preferred monomer unit (A2) is the following monomer unit: In formula (A2), R 2 and R 3 Each of the following independently represents a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group, R. 4 and R 5 Each can be used to represent a fluorine atom or a trifluoromethyl group independently.

[0127] A more preferred monomer unit (A2) is the following monomer unit: In formula (A2), R 2 R represents a fluorine atom. 3 R represents a fluorine atom, trifluoromethyl, or trifluoromethoxy group. 4 and R 5 Each can be used to represent a fluorine atom or a trifluoromethyl group independently.

[0128] The particularly preferred monomer unit (A2) is the following monomer unit: In formula (A2), R 2 R represents a fluorine atom. 3 R represents a fluorine atom or trifluoromethoxy group. 4 and R 5 The same indicates a fluorine atom or a trifluoromethyl group.

[0129] A preferred example of a single-unit (A2) includes a single-unit shown in the following formula (sometimes referred to in this specification as "single-unit (A2-1)" and "single-unit (A2-2)" respectively).

[0130] and In the single-unit cell (A3), R 6 ~R 9 Each can be independent and can be a fluorine atom, a C1-C3 straight-chain or branched perfluoroalkyl group, or a C1-C3 straight-chain or branched perfluoroalkoxy group. R 6 ~R 9Fluorine atoms, trifluoromethyl, perfluoroethyl, or trifluoromethoxy are preferred individually, with fluorine atoms, trifluoromethyl, or trifluoromethoxy being more preferred.

[0131] The preferred monomer unit (A3) is the following monomer unit: In formula (A3), R 6 ~R 9 Each can be used to represent a fluorine atom or a trifluoromethyl group independently.

[0132] A more preferred monomer unit (A3) is the following monomer unit: In formula (A3), R 6 ~R 9 R represents a fluorine atom. 6 ~R 8 Represents fluorine atom, R 9 R represents trifluoromethyl. 6 Indicates trifluoromethyl, R 7 ~R 9 Represents a fluorine atom, or R 6 and R 9 Indicates trifluoromethyl, R 7 and R 8 This represents a fluorine atom.

[0133] A preferred example of a single-unit (A3) includes a single-unit shown in the following formula (sometimes referred to as "single-unit (A3-1)" in this specification). In addition to the monomer units with fluorinated aliphatic rings included as the main component, fluoropolymers may also contain other monomer units. The proportion of these other monomer units in the total number of monomer units in the fluoropolymer may be less than 50 mol%, preferably less than 20 mol%, more preferably less than 10 mol%, and particularly preferably 0 mol%.

[0134] Other single-unit units may be listed as those shown in the following formula (A11) (sometimes referred to as "single-unit (A11)" in this specification), but are not limited thereto. [In the formula, R] 111 This indicates a fluorine atom, a C1-C6 perfluoroalkyl group, or a C1-C6 perfluoroalkoxy group. For example, fluoropolymers may contain monomer units (A2-1) and monomer units shown in the following formula (A11-1) (sometimes referred to as "monomer unit (A11-1)" in this specification). R 111 It can be a fluorine atom, a straight-chain or branched C1-C6 perfluoroalkyl group, or a straight-chain or branched C1-C6 perfluoroalkoxy group.

[0135] Preferred R 111 It is a fluorine atom, a straight-chain or branched C1-C4 perfluoroalkyl group, or a straight-chain or branched C1-C4 perfluoroalkoxy group.

[0136] More preferred R 111 It is a fluorine atom, a straight-chain or branched C1-C3 perfluoroalkyl group, or a straight-chain or branched C1-C3 perfluoroalkoxy group.

[0137] Specially selected R 111 It is a fluorine atom or a trifluoroalkyl group.

[0138] The monomer units included as the main component in the fluoropolymer can be -(CF2CF2)-, -(CHFCF2)-, -(CH2CF2)-, -(CH2CHF)-, -(CHFCHF)-, -(CF2CClF)-, -(CF2CFCF2-O-Rf)- (where Rf is a perfluoroalkyl group with 1 to 5 carbon atoms), etc., and can be -(CH2CF2)-, -(CF2CClF)-, etc. The proportion of these monomer units in the fluoropolymer is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.

[0139] The monomer units included as the main components in the fluoropolymer are preferably the monomer units shown in the above formula (A3-1), -(CF2CF2)-, -(CHFCF2)-, -(CH2CF2)-, -(CH2CHF)-, -(CHFCHF)- or -(CF2CClF)-.

[0140] The solvent for the fluoropolymer that is soluble in the solvent is the solvent (C) described above. Therefore, unless otherwise specified, the description of solvent (C) described below shall apply to this solvent.

[0141] Examples of solvent-soluble fluoropolymers include polyvinylidene fluoride (PVF), polyvinylidene fluoride (PVdF), vinylidene fluoride (VdF) / tetrafluoroethylene (TFE) copolymers, VdF / hexafluoropropylene (HFP) copolymers, VdF / TFE / HFP copolymers, VdF / HFP / (meth)acrylic acid copolymers, VdF / chlorotrifluoroethylene (CTFE) copolymers, VdF / pentafluoropropylene copolymers, VdF / perfluoro(alkyl vinyl ether) (PAVE) / TFE copolymers, polyfluoroalkyl allyl ethers, TFE / fluoroalkyl allyl ether copolymers, and amorphous perfluoropolymers. Fluoroalkyl allyl ethers are monomers represented by CF2=CFCF2-O-Rf (where Rf is a perfluoroalkyl group with 1 to 5 carbon atoms). Amorphous perfluoropolymers are perfluoropolymers that contain monomer units with fluorinated aliphatic rings as the main component and do not substantially have a crystalline structure.

[0142] The fluoropolymer of the present invention can be any of the solvent-soluble fluoropolymers listed above, wherein the polymerization site of the monomer constituting the fluoropolymer is a carbon atom, and the structure of the fluoropolymer has a nitrogen-containing aromatic ring.

[0143] The mass-average molecular weight of the fluoropolymer can be in the range of 5,000 to 2,000,000, 10,000 to 1,800,000, 10,000 to 1,500,000, 30,000 to 1,500,000, 50,000 to 1,350,000, etc., 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.

[0144] The lower limit of the mass-average molecular weight of fluoropolymers can be, for example, 5,000 or more, preferably 10,000 or more, more preferably 30,000 or more, and particularly preferably 50,000 or more. The upper limit of the mass-average molecular weight of fluoropolymers can be, for example, 2,000,000 or less, preferably 1,800,000 or less, more preferably 1,500,000 or less, and particularly preferably 1,350,000 or less. The above lower and upper limits can be appropriately combined.

[0145] The mass-average molecular weight of the fluoropolymer is a value determined using GPC (gel permeation chromatography) (especially the GPC method described in the examples).

[0146] Fluoropolymers can be synthesized using known methods. For example, they can be synthesized by polymerizing monomers corresponding to the structural units of the fluoropolymer. As polymerization methods, free radical polymerization, monolithic polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., can be used. The method for manufacturing the fluoropolymer of the present invention is preferred as the method for manufacturing the fluoropolymer.

[0147] Fluoropolymers containing nitrogen-containing aromatic rings can be used in applications where fluoropolymers (A) are used. Due to their high adhesion to metals, fluoropolymers containing nitrogen-containing aromatic rings can be used in applications such as encapsulation resins (e.g., encapsulation resins for optical components, encapsulation resins for semiconductor substrates), adhesives, especially adhesives for bonding protective films and frames, adhesives for bonding fluoropolymer liners and metal substrates, etc.

[0148] One embodiment of the present invention is an encapsulating resin containing a fluoropolymer having a nitrogen-containing aromatic ring.

[0149] One embodiment of the present invention is a fluoropolymer adhesive containing a fluoropolymer having a nitrogen-containing aromatic ring. This fluoropolymer adhesive can be used for bonding protective films and frames, and for bonding fluoropolymer liners and metal substrates.

[0150] One embodiment of the present invention is an optical device containing the above-described encapsulating resin or the above-described fluororesin adhesive.

[0151] One embodiment of the present invention is a protective member comprising a protective film and a frame, the protective member containing a fluoropolymer having a nitrogen-containing aromatic ring. The protective member may be constructed by bonding the protective film and the frame with the aforementioned fluoropolymer adhesive.

[0152] One embodiment of the present invention is an exposure processing method, which is an exposure processing method in photolithography using a light source with an emission wavelength of less than 200 nm, and uses the aforementioned protective member. In this exposure processing method, the light source with a wavelength of less than 200 nm can be a fluorine excimer laser or a fluorine excimer laser.

[0153] Method for manufacturing fluoropolymers with nitrogen-containing aromatic rings Fluoropolymers having nitrogen-containing aromatic rings can be manufactured by reacting a fluoropolymer (A) containing a monomer unit having a fluorinated aliphatic ring as the main component with a reactive reagent (B) having a nitrogen-containing aromatic ring in a solvent (C) (preferably an aprotic solvent).

[0154] Fluoropolymer (A) Fluoropolymer (A) comprises a monomer unit having a fluorinated aliphatic ring as its main component. Except for lacking a nitrogen-containing aromatic ring and a linker group, fluoropolymer (A) can be the same polymer as the fluoropolymer described above that comprises a monomer unit having a fluorinated aliphatic ring as its main component. Therefore, the various descriptions above regarding fluoropolymers comprising a monomer unit having a fluorinated aliphatic ring as its main component are applicable to fluoropolymer (A). Fluoropolymer (A) can be manufactured using known methods, such as the method described in International Publication No. 2021 / 085349.

[0155] The terminal group of the fluoropolymer (A) can be a group corresponding to the polymerization initiator used in the manufacture of the fluoropolymer (A). This terminal group is, for example, a group (K) shown in the following formula (K), but is not limited thereto. Alternatively, in the manufacturing method of the present invention, the terminal group of the fluoropolymer (A) can also be -COF. The terminal groups can be the same or different. [In the formula, v represents 0 or 1, R] 40 Indicates alkyl or alkoxy. R 40 The alkyl group can be C1-C6 alkyl, C1-C5 alkyl, etc., preferably C1-C4 alkyl, and more preferably C1-C3 alkyl. The alkyl group can be straight-chain or branched.

[0156] R 40 The alkoxy group can be C1-C6 alkoxy, C1-C5 alkoxy, etc., preferably C1-C4 alkoxy, and more preferably C1-C3 alkoxy. The alkoxy group can be straight-chain or branched.

[0157] R 40 For example, it can be a straight-chain or branched C1-C6 alkyl, or a straight-chain or branched C1-C6 alkoxy, a straight-chain or branched C1-C5 alkyl, or a straight-chain or branched C1-C5 alkoxy, etc., preferably a straight-chain or branched C1-C4 alkyl, or a straight-chain or branched C1-C4 alkoxy, more preferably a straight-chain or branched C1-C3 alkyl, or a straight-chain or branched C1-C3 alkoxy.

[0158] Compared to alkyl groups, R 40 Alkyl groups are preferred. R 40 The alkyl and alkoxy groups in it do not contain ether bonds.

[0159] The aforementioned terminal group can be a COF group or a -CF2-O-CO-O-n-propyl group.

[0160] In this invention, a nitrogen-containing aromatic ring can be introduced into the fluoropolymer (A) by reacting a fluoropolymer (A) having these terminal groups, preferably with terminal groups (K) or -COF, in a solvent (C) with a reactive reagent (B). When using a fluoropolymer (A) with terminal groups (K), the recovery step to -COF can be omitted. An example of the reaction step is summarized below. In the reaction step, the solvent (C) is omitted. In existing methods, the fluoropolymer (A) is heated to form -COF terminals, followed by hydrolysis, but this generates hydrofluoric acid as a byproduct. In the manufacturing method of this invention, water is not required, thus preventing or reducing the formation of hydrofluoric acid byproducts.

[0161] Reactive reagents with nitrogen-containing aromatic rings (B) Reactive reagents (B) with nitrogen-containing aromatic rings can be nucleophiles.

[0162] Reactive reagents (B) containing nitrogen-containing aromatic rings can be, for example, 1-(3-aminopropyl)imidazolium, 4-(1H-benzimidazol-2-yl)aniline, 2-aminobenzimidazolium, 5-aminobenzimidazolium, 5-amino-2-mercaptobenzimidazolium, 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-methyl-6-(methylamino)-1,3,5-triazine, 2,4-diamino-6-butylamino-1,3,5-triazine, 2-amino-4-methoxy-6-methyl-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, cyanuric acid monoamide, cyanuric acid diamide, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-isopropoxy -1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2-aminopurine, 8-azaadenine, 6-O-methylguanine, 2,6-diaminopurine, N-methoxy-7H-purine-6-amine, 1H-1,2,4-triazol-3-thiol, 4-methyl-4H-1,2,4-triazol-3-thiol, 2-mercaptobenzimidazole, 2-mercapto-1-methylbenzimidazole, 5-ethoxy-2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole 2-Mercapto-5-methoxybenzimidazole, trithiocyanate, 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 6-mercaptopurine, 2-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 1H-benzotriazole-1-methanol, 2-aminooxazole, 5-amino-3-methylisooxazole, 3-hydroxy-5-methylisooxazole, muscarinic acid, 3-amino-5-tert-butylisooxazole, 2-aminobenzoxazole, 2-mercaptobenzoxazole.

[0163] Reactive reagents (B) containing nitrogen-containing aromatic rings can be, for example, 1-(3-aminopropyl)imidazolium, 4-(1H-benzimidazol-2-yl)aniline, 2-aminobenzimidazolium, 5-aminobenzimidazolium, 3-amino-1H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 1-aminobenzotriazole, 2-aminobenzotriazole, 1H-1,2,3-benzotriazole-5-amine, 5-aminobenzotriazole, 2-amino-4-methoxy-6-methyl-1,3,5-triazine, 2-aminopurine, 8-azaadenine, N -Methoxy-7H-purine-6-amine, 1H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-mercaptobenzimidazole, 2-mercapto-1-methylbenzimidazole, 2-mercapto-5-methylbenzimidazole, trithiocyanate, 6-mercaptopurine, 2-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 1H-benzotriazole-1-methanol, 2-aminooxazole, 5-amino-3-methylisooxazole, 3-hydroxy-5-methylisooxazole, 2-aminobenzoxazole, 2-mercaptobenzoxazole.

[0164] The reactive reagent (B) having a nitrogen-containing aromatic ring can be at least one of the compounds shown in the following formula. Solvent (C) The compositions of the present invention contain a solvent (C). Preferably, the solvent (C) is an aprotic solvent. At least one selected from perfluorinated solvents and non-perfluorinated solvents can be included as the aprotic solvent.

[0165] Perfluorinated solvents are aprotic solvents containing fluorine and carbon atoms but no hydrogen atoms. Examples of perfluorinated solvents include perfluorinated aromatic compounds, perfluorinated trialkylamines, perfluorinated alkanes, and perfluorinated cyclic ethers. Perfluorinated solvents can be used alone or in combination of two or more.

[0166] Non-perfluorinated solvents are aprotic solvents containing fluorine, carbon, and hydrogen atoms. Examples of non-perfluorinated solvents include hydrofluorocarbons, hydrofluoroethers, and olefin compounds containing at least one chlorine atom. Non-perfluorinated solvents can be used alone or in combination of two or more. Non-perfluorinated solvents are preferred solvents because they can dissolve polymers with low solubility, which contain structural units (A3) as the main component, at high concentrations.

[0167] Perfluoroaromatic compounds are, for example, perfluoroaromatic compounds that may have one or more perfluoroalkyl groups. The aromatic rings of a perfluoroaromatic compound may be at least one ring selected from benzene rings, naphthalene rings, and anthracene rings. Perfluoroaromatic compounds may also have one or more (e.g., one, two, or three) aromatic rings.

[0168] The perfluoroalkyl group used as a substituent is, for example, a straight-chain or branched C1-C6, C1-C5, or C1-C4 perfluoroalkyl group, preferably a straight-chain or branched C1-C3 perfluoroalkyl group, and more preferably a trifluoromethyl or pentafluoroethyl group.

[0169] The number of substituents is, for example, 1 to 4, preferably 1 to 3, and more preferably 1 to 2. When multiple substituents are present, they can be the same or different.

[0170] Examples of perfluoroaromatic compounds include perfluorobenzene, perfluorotoluene, perfluoroxylene, and perfluoronaphthalene.

[0171] Preferred examples of perfluoroaromatic compounds include perfluorobenzene and perfluorotoluene.

[0172] Perfluorotrialkylamines are amines, for example, substituted with three straight-chain or branched perfluoroalkyl groups. The perfluoroalkyl group has, for example, 1 to 10 carbon atoms, preferably 1 to 5, more preferably 1 to 4. The perfluoroalkyl group may be the same or different, but is preferably the same.

[0173] Examples of perfluorotrialkylamines include perfluorotrimethylamine, perfluorotriethylamine, perfluorotri-n-propylamine, perfluorotriisopropylamine, perfluorotri-n-butylamine, perfluorotri-sec-butylamine, perfluorotri-tert-butylamine, perfluorotri-n-pentylamine, perfluorotriisopentylamine, and perfluorotrinepentylamine.

[0174] Preferred examples of perfluorotrialkylamines include perfluorotripropylamine and perfluorotributylamine.

[0175] Perfluoroalkanes are, for example, straight-chain, branched, or cyclic C3-C12 (preferably C3-C10, more preferably C3-C6) perfluoroalkanes.

[0176] Examples of 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 perfluorodecahydronaphthalene.

[0177] Preferred examples of perfluoroalkanes include perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane.

[0178] Hydrofluorocarbons (HFCs) are, for example, C3-C8 HFCs. Examples of HFCs include CF3CH2CF2H, CF3CH2CF2CH3, CF3CHFCHFC2F5, 1,1,2,2,3,3,4-heptafluorocyclopentane, CF3CF2CF2CF2CH2CH3, CF3CF2CF2CF2CF2CHF2, and CF3CF2CF2CF2CF2CF2CH2CH3.

[0179] Preferred examples of hydrofluorocarbons include CF3CH2CF2H and CF3CH2CF2CH3.

[0180] Perfluorocyclic ethers are, for example, perfluorocyclic ethers having one or more perfluoroalkyl groups. The rings in a perfluorocyclic ether can be 3- to 6-membered rings. The rings in a perfluorocyclic ether can have one or more oxygen atoms as cyclic atoms. Preferably, the ring has one or two, more preferably one oxygen atom.

[0181] The perfluoroalkyl group used as a substituent is, for example, a straight-chain or branched C1-C6, C1-C5, or C1-C4 perfluoroalkyl group. Preferred perfluoroalkyl groups are straight-chain or branched C1-C3 perfluoroalkyl groups.

[0182] The number of substituents is, for example, 1 to 4, preferably 1 to 3, and more preferably 1 to 2. When multiple substituents are present, they can be the same or different.

[0183] Examples of perfluorocyclic ethers include perfluorotetrahydrofuran, perfluoro-5-methyltetrahydrofuran, perfluoro-5-ethyltetrahydrofuran, perfluoro-5-propyltetrahydrofuran, perfluoro-5-butyltetrahydrofuran, and perfluorotetrahydropyran.

[0184] Preferred examples of perfluorocyclic ethers include perfluoro-5-ethyltetrahydrofuran and perfluoro-5-butyltetrahydrofuran.

[0185] Hydrofluoroethers are, for example, fluorinated ethers.

[0186] The global warming potential (GWP) of hydrofluoroethers is preferably below 600, more preferably below 400, and particularly preferably below 300. The lower limit of the GWP of hydrofluoroethers can be above 1 or above 5.

[0187] Examples of hydrofluoroethers include CF3CF2CF2CF2OCH3, CF3CF2CF(CF3)OCH3, CF3CF(CF3)CF2OCH3, (CF3)2CFCF2OCH3, CF3CF2CF2CF2OC2H5, (CF3)2CFCF2OC2H5, CF3CH2OCF2CHF2, C2F5CF(OCH3)C3F7, (CF3)2CHOCH3, (CF3)2CFOCH3, CHF2CF2OCH2CF3, CHF2CF2CH2OCF2CHF2, CF3CHFCF2OCH3, CF3CHFCF2OCF3, and trifluoromethyl 1,2,2, 2-Tetrafluoroethyl ether (HFE-227me), difluoromethyl 1,1,2,2,2-pentafluoroethyl ether (HFE-227mc), trifluoromethyl 1,1,2,2-tetrafluoroethyl ether (HFE-227pc), difluoromethyl 2,2,2-trifluoroethyl ether (HFE-245mf), 2,2-difluoroethyltrifluoromethyl ether (HFE-245pf), 1,1,2,3,3-hexafluoropropylmethyl ether (CF3CHFCF2OCH3), 1,1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (CHF2CF2OCH2CF3), and 1,1,1,3,3,3-hexafluoro-2-methoxypropane ((CF3)2CHOCH3).

[0188] Preferred examples of hydrofluoroethers include CF3CF2CF2CF2OCH3, (CF3)2CFCF2OCH3, CF3CF2CF2CF2OC2H5, (CF3)2CFCF2OC2H5, CF3CH2OCF2CHF2, C2F5CF(OCH3)C3F7, 1,1,2,3,3-hexafluoropropylmethyl ether (CF3CHFCF2OCH3), 1,1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (CHF2CF2OCH2CF3), and 1,1,1,3,3,3-hexafluoro-2-methoxypropane ((CF3)2CHOCH3).

[0189] The hydrofluoroether can be at least one of the following compounds: (C-1), (C-2), (C-3), (C-4), (CF3)2CHOCH3, (CF3)2CFOCH3, CF3CHFCF2OCH3, and CF3CHFCF2OCF3.

[0190] Equation (C-1): F(CF2) p O(CH2) q H (C-1) [In the formula, p is an integer from 1 to 6, and q is an integer from 1 to 4.] Equation (C-2): H(CF2) p O(CF2) q F (C-2) [In the formula, p and q have the same meanings as described above.] Equation (C-3): H(CF2) p O(CH2) q H (C-3) [In the formula, p and q have the same meanings as described above.] Equation (C-4): X (CF2) p CH2O(CF2) q H (C-4) [In the formula, X represents a fluorine atom or a hydrogen atom, and the meanings of p and q are the same as above.] Hydrofluoroethers are more preferably compounds represented by the following formula (C-5).

[0191] R 21 -O-R 22 (C-5) [In the formula, R] 21 R is a straight-chain or branched propyl or butyl group in which one or more hydrogen atoms are replaced by fluorine atoms. 22 It is either methyl or ethyl. The compound represented by formula (C-5) can be R 21 It is perfluorobutyl, and R 22 Compounds that are methyl or ethyl.

[0192] An olefin compound containing at least one chlorine atom is a C2-C4 (preferably C2-C3) olefin compound whose structure contains at least one chlorine atom. An olefin compound containing at least one chlorine atom is a compound in which at least one of the hydrogen atoms bonded to the carbon atoms in a hydrocarbon having 2 to 4 carbon atoms with one or two (preferably one) double bonds is replaced by a chlorine atom.

[0193] The number of chlorine atoms ranges from 1 to the maximum number that can be substituted. For example, the number of chlorine atoms can be 1, 2, 3, 4, 5, etc.

[0194] Alkene compounds containing at least one chlorine atom may also contain at least one (e.g., one, two, three, four, five, etc.) fluorine atom.

[0195] Examples of alkenes containing at least one chlorine atom include CH2=CHCl, CHCl=CHCl, CCl2=CHCl, CCl2=CCl2, CF3CH=CHCl, CHF2CF=CHCl, CFH2CF=CHCl, CF3CCl=CFCl, CF2HCl=CFCl, and CFH2Cl=CFCl.

[0196] Preferred examples of olefin compounds containing at least one chlorine atom include CHCl=CHCl, CHF2CF=CHCl, CF3CH=CHCl, and CF3CCl=CFCl.

[0197] Hydrofluoroethers are preferred as a nonprotic solvent, considering their low environmental impact during use and ease of removal from polymers by distillation.

[0198] The solvent (C) is preferably selected from at least one of perfluorobenzene, (CF3)2CFCF2OCH3, CF3CF2CF2CF2OCH3, (CF3)2CFCF2OC2H5 and CF3CF2CF2CF2OC2H5.

[0199] The global warming potential (GWP) of aprotic solvents can be below 600, below 400, etc., preferably below 375, more preferably below 350, and particularly preferably 0. The lower limit of the global warming potential (GWP) of aprotic solvents can be above 1 or above 5.

[0200] The process of reacting a fluoropolymer (A) with a reactive reagent (B) having a nitrogen-containing aromatic ring in a solvent (C). Regarding the amount of reactive reagent (B) used in the reaction, for example, relative to the mass of the fluoropolymer (A), it can be more than 0.01% by mass, more than 0.05% by mass, more than 0.1% by mass, 0.1 to 100% by mass, 0.1 to 50% by mass, or 0.1 to 20% by mass.

[0201] The amount of solvent (C) used in this reaction can be an amount sufficient to function as a solvent, based on common technical knowledge. For example, relative to the mass of the fluoropolymer (A), it can 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.

[0202] The reaction temperature can be, for example, -20 to 120°C, 0 to 100°C, or 5 to 80°C. The reaction time can be, for example, 0.01 to 48 hours, 0.1 to 48 hours, or 0.1 to 24 hours.

[0203] This reaction can be carried out in the presence of an inert gas (e.g., nitrogen) or in the absence of an inert gas. It can be carried out under reduced pressure, atmospheric pressure, or pressurized conditions.

[0204] Depending on the requirements, the fluoropolymers with nitrogen-containing aromatic rings generated in this reaction can be separated or purified using common methods or combinations thereof, such as extraction, dissolution, concentration, filtration, precipitation, dehydration, adsorption, and chromatography.

[0205] Compositions containing a fluoropolymer with a nitrogen-containing aromatic ring and hydrogen fluoride. One embodiment of the present invention is a composition comprising a fluoropolymer having a nitrogen-containing aromatic ring and hydrogen fluoride. In the composition, the content of hydrogen fluoride can be 0.005 ppm to 50 ppm relative to the content of the fluoropolymer having a nitrogen-containing aromatic ring. The composition of the present invention has a low hydrogen fluoride content, and the manufacturing method of the present invention can reduce manufacturing costs, thus enabling it to be effectively used as a supply source of the fluoropolymer having a nitrogen-containing aromatic ring. The composition of the present invention can be manufactured, for example, by the manufacturing method of the present invention. The above description regarding the fluoropolymer having a nitrogen-containing aromatic ring in the composition of the present invention is applicable.

[0206] The content of hydrogen fluoride in the composition can be 0.005 ppm to 50 ppm or 0.005 ppm to 10 ppm, relative to the content of the fluoropolymer with nitrogen-containing aromatic rings.

[0207] In addition to a fluoropolymer with a nitrogen-containing aromatic ring and hydrogen fluoride, the composition may contain other components. The amounts of the various components 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). Furthermore, the amounts of these various components can be adjusted by refining the fluoropolymer after manufacturing the nitrogen-containing aromatic ring.

[0208] Other components mentioned above include, for example, the reactive reagent (B) mentioned above, the byproduct alcohol generated when the terminal group reacts with the reactive reagent (B), and the salt obtained by reacting the reactive reagent (B) with hydrogen fluoride.

[0209] Alcohols that are byproducts formed when the terminal group reacts with the reactive reagent (B) can be listed as MeOH, EtOH, n-PrOH, i-PrOH, n-BuOH, s-BuOH, t-BuOH, 1-undecaneol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 4-tert-butylcyclohexanol, etc.

[0210] Salts obtained by reacting reactive reagent (B) with hydrogen fluoride include, for example, 1-(3-aminopropyl)imidazolium hydrofluoride, 4-(1H-benzimidazol-2-yl)aniline hydrofluoride, 2-aminobenzimidazolium hydrofluoride, 5-aminobenzimidazolium hydrofluoride, 3-amino-1H-1,2,4-triazole hydrofluoride, 4-amino-1,2,4-triazole hydrofluoride, 4-amino-4H-1,2,4-triazole hydrofluoride, 1-aminobenzotriazole hydrofluoride, 2-aminobenzotriazole hydrofluoride, 1H-1,2,3-benzotriazole-5-amine hydrofluoride, 5-aminobenzotriazole hydrofluoride, and 2-amino-4-methoxy-6-methyl-1,3,5-triazine hydrofluoride. 2-Aminopurine hydrofluoric acid, 8-azaadenine hydrofluoric acid, N-methoxy-7H-purine-6-amine hydrofluoric acid, 2-mercaptobenzimidazole hydrofluoric acid, 2-mercapto-1-methylbenzimidazole hydrofluoric acid, 2-mercapto-5-methylbenzimidazole hydrofluoric acid, 6-mercaptopurine hydrofluoric acid, 2-hydroxybenzimidazole hydrofluoric acid, 2-(hydroxymethyl)benzimidazole hydrofluoric acid, 2-(3-hydroxypropyl)benzimidazole hydrofluoric acid, 1H-benzotriazole-1-methanol hydrofluoric acid, 2-aminooxazole hydrofluoric acid, 5-amino-3-methylisooxazole hydrofluoric acid, 3-hydroxy-5-methylisooxazole hydrofluoric acid, 2-aminobenzooxazole hydrofluoric acid, 2-mercaptobenzimidazole hydrofluoric acid, etc.

[0211] When the composition contains other components, their content relative to the content of the fluoropolymer having a nitrogen-containing aromatic ring can be 0.1 ppm to 100 ppm or 0.1 ppm to 10 ppm.

[0212] The implementation methods have been described above, but it should be understood that various changes can be made to the methods and details as long as they do not depart from the spirit and scope of the claims of this invention.

[0213] Example Hereinafter, one embodiment of the present invention will be described in more detail using examples, etc., but the present invention is not limited to these.

[0214] The materials, terminology, measurement methods, etc. used in the examples are described below.

[0215] (Monomer units of fluoropolymers) The molar ratio of tetrafluoroethylene units to perfluoropropoxyethylene units in polymer 1 is 98:2. (End structure of fluoropolymers) n-Pr represents n-propyl. (Reactive reagents) (solvent) PFB: Perfluorobenzene HFE7100: Hydrofluoroether (Novec 7100 manufactured by 3M) HFE7200: Hydrofluoroether (Novec 7200 manufactured by 3M) NMP: N-methyl-2-pyrrolidone water (Method for determining hydrogen fluoride content) Place 0.1g to 5.0g of the fluoropolymer into a 1 / 4-inch straight-through fitting manufactured by Swagelok, and seal both ends with caps. Heat at 270°C for 30 minutes, allow to cool, and then open one cap. Determine the hydrogen fluoride content using a 17L hydrogen fluoride gas detection tube manufactured by GASTEC. Calculate the weight of the hydrogen fluoride based on the measurement results and the gas's equation of state. Calculate the hydrogen fluoride content in the polymer based on the ratio of the hydrogen fluoride content to the weight of the polymer used for measurement.

[0216] Comparative Example 1 1 g of polymer 1 with terminal structure 1 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for one day. After one day, the polymer's dissolution status was checked; a white solid remained, indicating no dissolution. 0.1 g of reactive reagent 1 was added, and the mixture was stirred at 50°C for one day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for one day. The resulting polymer was used to form a film, and IR was measured. The results confirmed that the terminal structure remained unchanged before and after the addition of the reactive reagent.

[0217] Comparative Example 2 1 g of polymer 1 with terminal structure 2 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for one day. After one day, the polymer's dissolution status was checked; a white solid remained, indicating no dissolution. 0.1 g of reactive reagent 1 was added, and the mixture was stirred at 50°C for one day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for one day. The resulting polymer was used to form a film, and IR was measured. The results confirmed that the terminal structure remained unchanged before and after the addition of the reactive reagent.

[0218] Comparative Example 3 1 g of polymer 2 with terminal structure 2 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for one day. After one day, the polymer's dissolution status was checked; a white solid remained, indicating no dissolution. 0.1 g of reactive reagent 1 was added, and the mixture was stirred at 50°C for one day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for one day. The resulting polymer was used to form a film, and IR was measured. The results confirmed that the terminal structure remained unchanged before and after the addition of the reactive reagent.

[0219] Comparative Example 4 1g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5g of water. The mixture was stirred at 50°C for 1 day. After 1 day, the dissolution state of the polymer was checked; a white solid remained, indicating no dissolution. Furthermore, the pH was measured using pH paper, showing a value of 1-2, thus indicating the presence of hydrofluoric acid. The solvent was removed by distillation, and the polymer was thoroughly washed with acetone and dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 1 (1880 cm⁻¹) was observed. -1 The peak disappeared, and a new peak (1809 cm⁻¹) was discovered, which can be considered to be the end of the COOH group. -1 1772cm -1 ).

[0220] Example 1 1 g of polymer 2 with terminal structure 1 was added to a glass vial, followed by 5 g of NMP, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and homogeneous. 0.1 g of reactive reagent 1 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 1 (1880 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1613 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 1. -1 3341cm -1 The HF content is 0.04 ppm. The end structure of this polymer is as follows. Example 2 1 g of polymer 2 with terminal structure 2 was added to a glass vial, followed by 5 g of NMP, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 1 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 2 (1830 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1613 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 1. -1 3341cm -1 The HF content is 0.08 ppm. The end structure of this polymer is as follows. Example 3 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and homogeneous. 0.1 g of reactive reagent 1 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1681 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 1. -1 3129cm -1 The HF content is 0.01 ppm. The end structure of this polymer is as follows. Example 4 Add 1g of polymer 3 with terminal structure 2 to a glass vial, then add 5g of PFB and stir for 1 day. After 1 day, confirm solubility; the polymer is completely dissolved and forms a homogeneous solution. Add 0.1g of reactive reagent 1 and stir at 50°C for 1 day. After stirring, distill to remove the solvent and reactive reagent. Wash the polymer thoroughly with acetone and dry it at 80°C under reduced pressure for 1 day. Allow the obtained polymer to form a film, and measure the IR. The peak from terminal structure 2 (1810 cm⁻¹) is the result. -1 The peak disappeared, and a peak (1681 cm⁻¹) was found that could be attributed to a group introduced by reactive reagent 1. -1 3129cm -1 The HF content is 1.64 ppm. The end structure of this polymer is as follows. Example 5 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 2 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1627 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 2. -1 3099cm -1 The HF content is 0.33 ppm. The end structure of this polymer is as follows. Example 6 1 g of polymer 3 with terminal structure 2 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 2 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 2 (1810 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1627 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 2. -1 3099cm -1 The HF content is 0.65 ppm. The end structure of this polymer is as follows. Example 7 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 3 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1643 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 3. -1 3104cm -1The HF content is 0.33 ppm. The end structure of this polymer is as follows. Example 8 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of PFB, and the mixture was stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 4 was added, and the mixture was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and then dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1528 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 4. -1 The HF content is 2.46 ppm. The end structure of this polymer is as follows. Example 9 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of HFE7100, and stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 1 was added, and the solution was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR spectrum was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1681 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 1. -1 3129cm -1 The HF content is 0.16 ppm. The end structure of this polymer is as follows. Example 10 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of HFE7100, and stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and homogeneous. 0.1 g of reactive reagent 4 was added, and the solution was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1528 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 4.-1 The HF content is 0.49 ppm. The end structure of this polymer is as follows. Example 11 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of HFE7200, and stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 1 was added, and the solution was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1681 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 1. -1 3129cm -1 The HF content is 3.27 ppm. The end structure of this polymer is as follows. Example 12 1 g of polymer 3 with terminal structure 1 was added to a glass vial, followed by 5 g of HFE7200, and stirred for 1 day. After 1 day, the polymer was confirmed to be completely dissolved and a homogeneous solution was formed. 0.1 g of reactive reagent 4 was added, and the solution was stirred at 50°C for 1 day. After stirring, the solvent and reactive reagent were removed by distillation. The polymer was thoroughly washed with acetone and dried at 80°C under reduced pressure for 1 day. The resulting polymer was used to form a film, and the IR was measured. The peak from terminal structure 1 (1882 cm⁻¹) was observed. -1 The peak disappeared, and a peak (1528 cm⁻¹) was found that could be attributed to a newly introduced group due to reactive reagent 4. -1 The HF content is 0.04 ppm. The end structure of this polymer is as follows.

Claims

1. A fluoropolymer, characterized in that: The fluoropolymer is soluble in a solvent, the polymerization site of the monomers constituting the fluoropolymer is a carbon atom, and the structure of the fluoropolymer contains a nitrogen-containing aromatic ring.

2. The fluoropolymer as described in claim 1, characterized in that: The nitrogen-containing aromatic ring is selected from at least one of the nitrogen-containing aromatic ring (1) shown in formula (1), nitrogen-containing aromatic ring (2) shown in formula (2), and nitrogen-containing aromatic ring (3) shown in formula (3). In equation (1), A represents an oxygen atom, a sulfur atom, or a substituent R. 10 The substituted nitrogen atom, R 10 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. X 1 ~X 4 In the alphabet, any one of the X's represents a carbon atom, and the other X's independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. The alkyl group, when present in multiple forms, may independently contain C1-C5 ether bonds and may be substituted with one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. In equation (2), Y 1 ~Y 6 In the first case, any one of the Y atoms represents a carbon atom, and the other Y atoms independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. The alkyl group, when present in multiple forms, may independently contain C1-C5 ether bonds and may be substituted with one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. In equation (3), B represents an oxygen atom, a sulfur atom, or a substituent R. 20 The substituted nitrogen atom, R 20 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. Z 1 ~Z 8 Any one of the Zs represents a carbon atom, and the other Zs independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. The alkyl group, when present in multiple forms, may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, or isocyanate groups.

3. The fluoropolymer as described in claim 1 or 2, characterized in that: The basic skeleton of the nitrogen-containing aromatic ring is selected from at least one of pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indoleazine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzoisoxazole, thiazole, isothiazole, benzothiazole, benzoisothiazole and purine.

4. The fluoropolymer as described in claim 1 or 2, characterized in that: The basic skeleton of the nitrogen-containing aromatic ring is selected from at least one of imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole and purine.

5. The fluoropolymer according to any one of claims 1 to 4, characterized in that: The fluoropolymer is a fluoropolymer containing a monomer unit with a fluorinated aliphatic ring as the main component. The fluorinated aliphatic ring of the fluoropolymer has one, two or three ether oxygen atoms as cyclizing atoms. When the fluorinated aliphatic ring contains multiple ether oxygen atoms, the ether oxygen atoms are not adjacent to each other. The structure of the fluoropolymer has a nitrogen-containing aromatic ring.

6. The fluoropolymer as described in claim 5, characterized in that: The monomer unit included as the main component in the fluoropolymer is the monomer unit (A1) shown in formula (A1), the monomer unit (A2) shown in formula (A2), or the monomer unit (A3) shown in formula (A3). In equation (A1), R 1 Indicates a fluorine atom or a C1-C5 perfluoroalkyl group. In equation (A2), R 2 ~R 5 Each of these can be independently represented by a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. In equation (A3), R 6 ~R 9 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.

7. The fluoropolymer as described in claim 6, characterized in that: The monomer unit included as the main component in the fluoropolymer is the monomer unit (A3).

8. The fluoropolymer as described in claim 6, characterized in that: The monomer units included as the main component in the fluoropolymer are monomer units (A1-1) shown in the following formula (A1-1), monomer units (A2-1) shown in the following formula (A2-1), monomer units (A2-2) shown in the following formula (A2-2), or monomer units (A3-1) shown in the following formula (A3-1). 。 9. The fluoropolymer as described in claim 8, characterized in that: The monomer unit included as the main component in the fluoropolymer is the monomer unit (A3-1).

10. The fluoropolymer according to any one of claims 1 to 5, characterized in that: The monomer units included as the main components in the fluoropolymer are -(CF2CF2)-, -(CHFCF2)-, -(CH2CF2)-, -(CH2CHF)-, -(CHFCHF)-, or -(CF2CClF)-.

11. The fluoropolymer according to any one of claims 1 to 10, characterized in that: The mass-average molecular weight of the fluoropolymer is in the range of 5,000 to 2,000,000.

12. The fluoropolymer according to any one of claims 1 to 10, characterized in that: The mass-average molecular weight of the fluoropolymer is in the range of 10,000 to 1,500,000.

13. The fluoropolymer according to claim 2, characterized in that: The connecting base has the structure shown in the following formula (L). In the formula, v represents 0 or 1, A represents an oxygen atom, a sulfur atom, -O-CH2-, or a nitrogen atom bonded to a hydrogen atom, methyl, ethyl, propyl, or isopropyl, and * represents the side bonded to a nitrogen-containing aromatic ring.

14. The fluoropolymer according to any one of claims 1 to 12, characterized in that: The nitrogen-containing aromatic ring is bonded to one or both of the monomer units at the end of the main chain of the fluoropolymer.

15. The fluoropolymer as described in claim 2, characterized in that: One of the carbon atoms constituting the nitrogen-containing aromatic ring is bonded to one or two monomer units at the end of the main chain of the fluoropolymer via a linker. The linker and nitrogen-containing aromatic ring bonded to one or two monomer units at the ends of the fluoropolymer backbone have any structure as shown in the following formula: ， The monomer units included as the main component in the fluoropolymer are monomer units represented by the following formula (A3-1): (A3-1), -(CF2CF2)-, -(CHFCF2)-, -(CH2CF2)-, -(CH2CHF)-, -(CHFCHF)-, or -(CF2CClF)-. 。 16. A method for manufacturing a fluoropolymer, characterized in that: The fluoropolymer comprises monomer units having fluorinated aliphatic rings as the main component, and the fluoropolymer has nitrogen-containing aromatic rings. The manufacturing method includes a step of reacting a fluoropolymer (A) containing monomer units having fluorinated aliphatic rings as the main component with a reactive reagent (B) having nitrogen-containing aromatic rings in a solvent (C). The fluorinated aliphatic ring has one, two, or three ether oxygen atoms as cyclizing atoms. When the fluorinated aliphatic ring contains multiple ether oxygen atoms, the ether oxygen atoms are not adjacent to each other.

17. The method for manufacturing a fluoropolymer as described in claim 16, characterized in that: The nitrogen-containing aromatic ring is selected from at least one of the nitrogen-containing aromatic ring (1) shown in formula (1), nitrogen-containing aromatic ring (2) shown in formula (2), and nitrogen-containing aromatic ring (3) shown in formula (3). In equation (1), A represents an oxygen atom, a sulfur atom, or a substituent R. 10 The substituted nitrogen atom, R 10 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. X 1 ~X 4 In the alphabet, any one of the X's represents a carbon atom, and the other X's independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. The alkyl group, when present in multiple forms, may independently contain C1-C5 ether bonds and may be substituted with one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. In equation (2), Y 1 ~Y 5 In the first case, any one of the Y atoms represents a carbon atom, and the other Y atoms independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. The alkyl group, when present in multiple forms, may independently contain C1-C5 ether bonds and may be substituted with one or more fluorine, hydroxyl, mercapto, amino, cyano, or isocyanate groups. In equation (3), B represents an oxygen atom, a sulfur atom, or a substituent R. 20 The substituted nitrogen atom, R 20 Indicates a fluorine atom, hydroxyl group, mercapto group, amino group, cyano group, isocyanate group, or alkyl group. Z 1 ~Z 8 Any one of the Zs represents a carbon atom, and the other Zs independently represent either a nitrogen atom or a carbon atom. At least one of the carbon atoms constituting the nitrogen-containing aromatic ring, when multiple are present, is independently bonded to the backbone of the fluorinated polymer via a linker group, or directly bonded to the backbone of the fluorinated polymer. Other carbon atoms constituting the nitrogen-containing aromatic ring can independently have substituents, even when multiple are present. When multiple substituents are present, they can independently be fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, isocyanate groups, or alkyl groups. The alkyl group, when present in multiple forms, may independently contain C1-C5 ether bonds and may be substituted by one or more fluorine atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, or isocyanate groups.

18. The method for manufacturing a fluoropolymer as described in claim 16 or 17, characterized in that: The basic skeleton of the nitrogen-containing aromatic ring is selected from at least one of pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole, indoleazine, benzimidazole, benzotriazole, oxazole, isoxazole, benzoxazole, benzoisoxazole, thiazole, isothiazole, benzothiazole, benzoisothiazole and purine.

19. The method for manufacturing a fluoropolymer as described in claim 16 or 17, characterized in that: The basic skeleton of the nitrogen-containing aromatic ring is selected from at least one of imidazole, triazole, triazine, benzimidazole, benzotriazole, oxazole, isoxazole and purine.

20. The method for manufacturing the fluoropolymer according to any one of claims 16 to 19, characterized in that: The reactive reagent (B) is selected from 1-(3-aminopropyl)imidazole, 4-(1H-benzimidazole-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-methyl-6-(methylamino)-1,3,5-triazine, 2,4-Diamino-6-butylamino-1,3,5-triazine, 2-Amino-4-methoxy-6-methyl-1,3,5-triazine, 2,4-Diamino-6-methyl-1,3,5-triazine, cyanuric acid monoamide, cyanuric acid diamide, 2,4-Diamino-1,3,5-triazine, 2,4-Diamino-6-isopropoxy-1,3,5- Triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2-aminopurine, 8-azaadenine, 6-O-methylguanine, 2,6-diaminopurine, N-methoxy-7H-purine-6-amine, 1H-1,2,4-triazol-3-thiol, 4-methyl-4H-1,2,4-triazol-3-thiol, 2-mercaptobenzimidazole, 2-mercapto-1-methylbenzimidazole, 5-ethoxy-2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-methylbenzimidazole At least one of the following: methoxybenzimidazole, trithiocyanate, 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 6-mercaptopurine, 2-hydroxybenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-(3-hydroxypropyl)benzimidazole, 1H-benzotriazole-1-methanol, 2-aminooxazole, 5-amino-3-methylisooxazole, 3-hydroxy-5-methylisooxazole, muscarinic acid, 3-amino-5-tert-butylisooxazole, 2-aminobenzoxazole, and 2-mercaptobenzoxazole.

21. The method for manufacturing the fluoropolymer according to any one of claims 16 to 20, characterized in that: The monomer unit included as the main component in the fluoropolymer (A) is the monomer unit (A1) shown in formula (A1), the monomer unit (A2) shown in formula (A2), or the monomer unit (A3) shown in formula (A3). In equation (A1), R 1 Indicates a fluorine atom or a C1-C5 perfluoroalkyl group. In equation (A2), R 2 ~R 5 Each of these can be independently represented by a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group. In equation (A3), R 6 ~R 9 Each of these can be independently represented as a fluorine atom, a C1-C5 perfluoroalkyl group, or a C1-C5 perfluoroalkoxy group.

22. The method for manufacturing a fluoropolymer as described in claim 21, characterized in that: The monomer unit included as the main component in the fluoropolymer (A) is the monomer unit (A3).

23. The method for manufacturing a fluoropolymer as described in claim 21, characterized in that: The monomer unit included as the main component in the fluoropolymer (A) is the monomer unit (A1-1) shown in the following formula (A1-1), the monomer unit (A2-1) shown in the following formula (A2-1), the monomer unit (A2-2) shown in the following formula (A2-2), or the monomer unit (A3-1) shown in the following formula (A3-1). 。 24. The method for manufacturing a fluoropolymer as described in claim 23, characterized in that: The monomer unit included as the main component in the fluoropolymer (A) is the monomer unit (A3-1).

25. The method for manufacturing the fluoropolymer according to any one of claims 16 to 24, characterized in that: The solvent (C) is an aprotic solvent.

26. The method for manufacturing a fluoropolymer as described in claim 25, characterized in that: The aprotic solvent is at least one solvent selected from perfluoroaromatic compounds, perfluorotrialkylamines, perfluoroalkanes, hydrofluorocarbons, perfluorocyclic ethers, hydrofluoroethers, and olefin compounds containing at least one chlorine atom.

27. The method for manufacturing a fluoropolymer as described in claim 25, characterized in that: The aprotic solvent is hydrofluoroether.

28. The method for manufacturing a fluoropolymer as described in claim 25, characterized in that: The global warming potential (GWP) of the aprotic solvent is below 400.

29. The method for manufacturing a fluoropolymer as described in claim 25, characterized in that: The aprotic solvent is at least one hydrofluoroether selected from the following compounds: (C-1), (C-2), (C-3), (C-4), (CF3)2CHOCH3, (CF3)2CFOCH3, CF3CHFCF2OCH3, and CF3CHFCF2OCF3. F(CF2) p O(CH2) q H (C-1) In equation (C-1), p is an integer from 1 to 6, and q is an integer from 1 to 4. H(CF2) p O(CF2) q F (C-2) In equation (C-2), the meanings of p and q are the same as above. H(CF2) p O(CH2) q H (C-3) In equation (C-3), the meanings of p and q are the same as above. X(CF2) p CH2O(CF2) q H (C-4) In formula (C-4), X represents a fluorine atom or a hydrogen atom, and the meanings of p and q are the same as above.

30. The method for manufacturing the fluoropolymer as described in claim 25, characterized in that: The aprotic solvent is a compound represented by formula (C-5). R 21 -O-R 22 (C-5) In equation (C-5), R 21 R is a straight-chain or branched propyl or butyl group in which one or more hydrogen atoms are replaced by fluorine atoms. 22 It can be methyl or ethyl.

31. The method for manufacturing the fluoropolymer according to any one of claims 16 to 30, characterized in that: The mass-average molecular weight of the fluoropolymer is in the range of 5,000 to 2,000,000.

32. The method for manufacturing the fluoropolymer according to any one of claims 16 to 30, characterized in that: The mass-average molecular weight of the fluoropolymer is in the range of 10,000 to 1,500,000.

33. The method for manufacturing the fluoropolymer according to any one of claims 16 to 32, characterized in that: The fluoropolymer (A) has at least one group selected from COF groups and groups (K) represented by the following formula (K). In the formula, v represents 0 or 1, and R 40 It indicates alkyl or alkoxy.

34. The method for manufacturing a fluoropolymer as described in claim 33, characterized in that: One or two of the monomer units at the end of the main chain of the fluoropolymer (A) have at least one group selected from the COF group and the group (K).

35. The method for manufacturing a fluoropolymer as described in claim 17, characterized in that: In a fluoropolymer comprising a monomer unit having the aforementioned 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 to one or two monomer units at the end of the main chain of the fluoropolymer via a linking group. The linker and nitrogen-containing aromatic ring bonded to one or two monomer units at the ends of the fluoropolymer backbone have any structure as shown in the following formula: ， The reactive reagent (B) is any compound represented by the following formula: ， The monomer unit included as the main component in the fluoropolymer (A) is the monomer unit (A3-1) shown in the following formula (A3-1). The terminal structure of the fluoropolymer (A) is -COF or -CF2-O-CO-O-n-propyl. The solvent (C) is selected from at least one of perfluorobenzene, (CF3)2CFCF2OCH3, CF3CF2CF2CF2OCH3, (CF3)2CFCF2OC2H5 and CF3CF2CF2CF2OC2H5.

36. An encapsulating resin, characterized in that: It contains the fluoropolymer as described in any one of claims 1 to 15.

37. A fluororesin adhesive, characterized in that: It contains the fluoropolymer as described in any one of claims 1 to 15.

38. The fluoropolymer adhesive as described in claim 37, characterized in that: Used for bonding the protective film to the frame.

39. An optical device, characterized in that: It contains any one of the encapsulating resin of claim 36, the fluoropolymer adhesive of claim 37, and the fluoropolymer adhesive of claim 38.

40. A protective component, characterized in that: Including protective film and frame, The protective component contains a fluoropolymer as described in any one of claims 1 to 15.

41. The protective member as described in claim 40, characterized in that: The protective film and the frame are bonded together by the fluoropolymer adhesive as described in claim 37.

42. An exposure processing method, characterized in that: It is an exposure processing method in photolithography using a light source with an emission wavelength below 200nm, and uses the protective component as described in claim 40.

43. The exposure processing method as described in claim 42, characterized in that: Light sources with wavelengths below 200nm are either fluorine excimer lasers or fluorine excimer lasers.

44. A composition, characterized in that: Contains the fluoropolymer and hydrogen fluoride as described in any one of claims 1 to 15. The content of hydrogen fluoride is 0.005 ppm to 50 ppm relative to the content of the fluoropolymer.

45. The composition according to claim 44, characterized in that: The content of hydrogen fluoride is 0.005 ppm to 10 ppm relative to the content of the fluoropolymer.

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