Tetrafluoroethylene-based polymer composition, binder for electrochemical device, electrode mixture, electrode, and secondary battery

Abstract

To provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device capable of reducing the resistance of the electrochemical device and also yielding a mixture sheet with excellent adhesion to a substrate and to provide a binder for the electrochemical device, an electrode mixture, an electrode, and a secondary battery, all using the same.SOLUTION: The tetrafluoroethylene-based polymer composition for use in a binder for an electrochemical device contains a polar group. The content of the polar group is less than 0.020 meq / g relative to the tetrafluoroethylene-based polymer composition. The composition is non-melt-processable and has an apparent density of less than 0.50 g / mL.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a tetrafluoroethylene-based polymer composition, a binder for an electrochemical device, an electrode binder, an electrode, and a secondary battery.

Background Art

[0002] Secondary batteries such as lithium-ion secondary batteries are used in small and portable electrical and electronic devices such as notebook computers, mobile phones, smartphones, tablet computers, and ultrabooks because of their high voltage, high energy density, low self-discharge, low memory effect, and ultra-lightweight. Furthermore, they are being put into practical use as a wide range of power sources, from in-vehicle power sources for driving such as those for automobiles to large stationary power sources. There is a demand for further increasing the energy density of secondary batteries and further improving battery characteristics.

[0003] Patent Document 1 describes an energy storage device in which at least one of a cathode and an anode contains a polytetrafluoroethylene mixed binder material.

[0004] Patent Documents 2 to 6 describe the use of polytetrafluoroethylene as a binder for a battery.

[0005] Patent Documents 7 to 9 describe the use of a vinylidene fluoride polymer as a binder for a battery.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0007] The present disclosure aims to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device, which can reduce the resistance of the electrochemical device and can also obtain an agent sheet excellent in adhesiveness to a substrate, and a binder for an electrochemical device, an electrode agent, an electrode, and a secondary battery using the same. [Means for Solving the Problems]

[0008] The present disclosure (1) is a tetrafluoroethylene-based polymer composition used for a binder for an electrochemical device, having a polar group, wherein the content of the polar group is less than 0.020 meq / g with respect to the tetrafluoroethylene-based polymer composition, being non-melt processable, and having an apparent density of less than 0.50 g / ml.

[0009] The present disclosure (2) is the tetrafluoroethylene-based polymer composition according to the present disclosure (1), having an apparent density of 0.35 g / ml or more and less than 0.50 g / ml.

[0010] The present disclosure (3) is the tetrafluoroethylene-based polymer composition according to the present disclosure (1) or (2), which is used for a binder for a lithium-ion secondary battery and is in powder form.

[0011] The present disclosure (4) is a binder for an electrochemical device consisting essentially of a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition has a polar group, the content of the polar group is less than 0.020 meq / g with respect to the tetrafluoroethylene-based polymer composition, is non-melt processable, and has an apparent density of less than 0.50 g / ml, which is a binder for an electrochemical device.

[0012] The present disclosure (5) is the binder for an electrochemical device according to the present disclosure (4), wherein the apparent density of the tetrafluoroethylene-based polymer composition is 0.35 g / ml or more and less than 0.50 g / ml.

[0013] The present disclosure (6) is the binder for an electrochemical device according to the present disclosure (4) or (5), wherein the polar group is at least one functional group selected from the group consisting of an amino group, a nitrile group, and an oxygen-containing polar group.

[0014] The present disclosure (7) is that the oxygen-containing polar group in the present disclosure (6) is a carbonyl group-containing group, an epoxy group, an oxetanyl group, -SO3X a , -SO2X a , -OSO2X a , -PO3X a , and -OX a (wherein X a is -H, a metal atom, -NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, an alkyl group, or a nitrile group. R 1 is H or an organic group.) is the binder for an electrochemical device according to the present disclosure (6), which is at least one functional group selected from the group consisting of.

[0015] The present disclosure (8) is the binder for an electrochemical device according to any one of the present disclosures (4) to (7), wherein the tetrafluoroethylene-based polymer is a copolymer of tetrafluoroethylene and a monomer having a polar group.

[0016] The present disclosure (9) is a binder for an electrochemical device according to any one of the present disclosures (4) to (8), wherein the tetrafluoroethylene-based polymer composition contains a fluorine-containing compound having a hydrophilic group.

[0017] The present disclosure (10) is such that the hydrophilic group is -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a , -OCOM a , and -OM a (wherein M a is -H, a metal atom, -NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 1 is H or an organic group.) The binder for an electrochemical device according to the present disclosure (9), which is at least one selected from the group consisting of

[0018] The present disclosure (11) is such that the fluorine-containing compound having a hydrophilic group is represented by the following general formula (N 0 ): X n0 -Rf n0 -Y 0 (N 0 ) (wherein X n0 is H, Cl or F. Rf n0 is an alkylene group having 3 to 20 carbon atoms, which is linear, branched or cyclic, and in which some or all of the H are substituted by F, and the alkylene group may contain one or more ether bonds and some of the H may be substituted by Cl. Y 0 is an anionic group.) The binder for an electrochemical device according to the present disclosure (9) or (10), which is a compound represented by

[0019] The present disclosure (12) is a binder for an electrochemical device according to any one of the present disclosures (9) to (11), wherein the fluorine-containing compound having the hydrophilic group is at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). General formula (1): (H-(CF2) m-1 -COO) p M 1 (In the formula, m is 4 to 20. M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is the same as above), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.)

[0020] The present disclosure (13) is a binder for an electrochemical device according to the present disclosure (9) or (10), wherein the fluorine-containing compound having the hydrophilic group is a polymer compound having an ionic group.

[0021] The present disclosure (14) is a binder for an electrochemical device according to the present disclosure (13), wherein the polymer compound is at least one selected from the group consisting of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II). General formula (I): CX 1 X 3 =CX 2 R(-CZ 1 Z2 -A 0 ) m (I) (wherein X 1 and X 3 are each independently F, Cl, H or CF3; A 0 is an anionic group; X 2 is H, F, an alkyl group or a fluorinated alkyl group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluorinated alkyl group; m is an integer of 1 or more.) General formula (II): T X -X A -R FA1 -R FA2 -X A -T X ’ (II) (wherein R FA1 is -Rf 1 p -R F -O q -; R FA2 is -Rf 2 p -R FX -O q -; R F is a divalent fluoropolyether group; R FX is a divalent fluoropolyether group containing an anionic group; Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms; p is each independently 0 or 1; q is each independently 0 or 1; X A are each independently a single bond or a group of 2 to 10 valences; T X and T X' is independently selected from the group consisting of (i) a C1-C 24 (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and has no anionic group, and (ii) a C1-C 24 (hydro)(fluoro)carbon group containing at least one of the anionic groups.)

[0022] The present disclosure (15) is a binder for an electrochemical device according to the present disclosure (14), wherein the polymer compound is a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I).

[0023] The present disclosure (16) is a binder for a lithium ion secondary battery, and is a binder for an electrochemical device according to any one of the present disclosures (4) to (15) which is in powder form.

[0024] The present disclosure (17) is an electrode mixture containing a tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (3), or a binder for an electrochemical device according to any one of the present disclosures (4) to (16) and an electrode active material.

[0025] The present disclosure (18) is an electrode mixture according to the present disclosure (17) which is in sheet form.

[0026] The present disclosure (19) is an electrode containing a tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (3), or a binder for an electrochemical device according to any one of the present disclosures (4) to (16), an electrode active material, and a current collector.

[0027] The present disclosure (20) is a secondary battery including the electrode according to the present disclosure (19).

Advantages of the Invention

[0028] According to the present disclosure, there are provided a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device, which can reduce the resistance of the electrochemical device and can obtain a paste sheet excellent in adhesiveness to a substrate, a binder for an electrochemical device using the same, an electrode paste, an electrode, and a secondary battery.

Brief Description of Drawings

[0029]

Figure 1

Embodiments for Carrying Out the Invention

[0030] In the present disclosure, the “organic group” means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. As the above organic group, an alkyl group which may have one or more substituents is preferable.

[0031] Hereinafter, the present disclosure will be specifically described.

[0032] The present disclosure provides a tetrafluoroethylene (TFE)-based polymer composition used for a binder for an electrochemical device, which has a polar group, the content of the polar group is less than 0.020 meq / g with respect to the TFE-based polymer composition, is non-melt processable, and has an apparent density of less than 0.50 g / ml.

[0033] By having the above configuration, the TFE-based polymer composition of the present disclosure can reduce the resistance of an electrochemical device when used as a binder for an electrochemical device, and can also obtain a paste sheet excellent in adhesiveness to a substrate (for example, a metal such as a current collector, a carbon coat layer, an electrode paste layer). In addition, the cycle characteristics of the electrochemical device can also be improved. The TFE-based polymer composition of the present disclosure can also be used dry, so it is not necessary to use a large amount of dispersion media such as water and organic solvents, and a wide range of electrode active materials and solid electrolytes to be combined can be selected, which is advantageous in the production process. In addition, the processes and costs due to the use of dispersion media can be reduced. Furthermore, since the TFE-based polymer composition of the present disclosure has excellent adhesion to active materials and electrolytes, the amount used can be reduced.

[0034] The TFE-based polymer composition of the present disclosure has a polar group. The above polar group is a group having polarity and includes hydrophilic groups and ionic groups described later. Examples of the above polar group include at least one functional group selected from the group consisting of an amino group, a nitrile group, and an oxygen-containing polar group. Among them, at least one selected from the group consisting of a nitrile group and an oxygen-containing polar group is preferable, and an oxygen-containing polar group is more preferable.

[0035] Examples of the above oxygen-containing polar group include a carbonyl group-containing group, an epoxy group, an oxetanyl group, -SO3X a , -SO2X a , -OSO2X a , -PO3X a , and -OX a (In the formula, X a is -H, a metal atom, -NR 1 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, an alkyl group, or a nitrile group. R 1 is H or an organic group.) and at least one functional group selected from the group consisting of. Among them, at least one selected from the group consisting of a carbonyl group-containing group, -SO3X a , and -OX a is preferable, and at least one selected from the group consisting of a carbonyl group-containing group and -SO3X a is more preferable. In addition, as the oxygen-containing polar group, -COOX a (In the formula, X ais the same as described above.) and -SO3X a It is also preferable that it is at least one selected from the group consisting of

[0036] Examples of the carbonyl group-containing group include -COOX a , -OCOX a (In the formula, X a is the same as described above.), a carbonate group, a halocarbonyl group, an acid anhydride residue, an isocyanate group, and the like. Among them, -COOX a , -OCOX a , and at least one selected from the group consisting of acid anhydride residues are preferable, and -COOX a , and at least one selected from the group consisting of acid anhydride residues are more preferable.

[0037] X a is -H, a metal atom, -NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, an alkyl group, or a nitrile group. Examples of the metal atom in X a include monovalent and divalent metal atoms, and examples include alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. The four Rs 1 may be the same or different. R 1 is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms. The carbon number of the alkyl group in X a is preferably 1 or more, preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less. The alkyl group may be linear or cyclic. When the alkyl group is cyclic, it corresponds to a cycloalkyl group. X a is preferably -H, an alkali metal atom, NH4, an alkyl group, or a nitrile group, more preferably -H, an alkali metal atom, NH4, or an alkyl group, and still more preferably -H, an alkali metal atom, or NH4.

[0038] The content of the above polar group is less than 0.020 meq / g with respect to the above TFE-based polymer composition. However, in terms of reducing resistance, improving adhesion to the substrate, and improving cycle characteristics, it is preferably 0.018 meq / g or less, more preferably 0.015 meq / g or less, still more preferably 0.012 meq / g or less, even more preferably 0.010 meq / g or less. Also, it is preferably 0.000001 meq / g or more, more preferably 0.000005 meq / g or more, still more preferably 0.00001 meq / g or more, even more preferably 0.00005 meq / g or more, and still more preferably 0.0001 meq / g or more. The content of the above polar group can be measured by ion chromatography or determined by calculation from the molecular weight per polar group.

[0039] The above polar group may be contained in the units constituting the above TFE-based polymer, may be contained in the end groups of the polymer main chain, or may be introduced into the above TFE-based polymer by plasma treatment or the like. Examples of the TFE-based polymer having the above polar group contained in the end groups of the polymer main chain include TFE-based polymers having a polar group as an end group derived from a polymerization initiator, a chain transfer agent, or the like. The above polar group may also be derived from a substance used in the polymerization of the above TFE-based polymer.

[0040] The above polar group can be introduced, for example, by copolymerizing TFE with a monomer having a polar group. It can also be introduced by polymerizing TFE in the presence of a non-fluorinated hydrocarbon-based surfactant, a fluorine-containing surfactant, or a polymer compound having an ionic group. Among these, it is preferably introduced by copolymerization. That is, the above TFE-based polymer is preferably a copolymer of TFE and a monomer having a polar group.

[0041] The above TFE-based polymer may be a homopolymer of TFE, or may be a TFE copolymer containing a polymerization unit based on TFE (TFE unit) and a polymerization unit based on a modified monomer copolymerizable with TFE (modified monomer unit). The above TFE-based polymer may be polytetrafluoroethylene (PTFE). The above PTFE includes a homopolymer of TFE and a modified PTFE containing 99.0% by mass or more of TFE units and 1.0% by mass or less of modified monomer units. The above TFE-based polymer is preferably PTFE, and more preferably modified PTFE, in terms of reducing resistance, improving adhesion to the substrate, and improving cycle characteristics, and in terms of obtaining a composite sheet excellent in strength and flexibility. In the present disclosure, the homopolymer of TFE refers to a polymer in which the content of the modified monomer unit is less than 0.0001% by mass based on all the polymerization units.

[0042] The content of the modified monomer unit is preferably in the range of 0.0001 to 10% by mass based on all the polymerization units, in terms of reducing resistance, improving adhesion to the substrate, and improving cycle characteristics, and in terms of obtaining a composite sheet excellent in strength and flexibility. As the lower limit of the content of the modified monomer unit, 0.001% by mass is more preferable, 0.005% by mass is still more preferable, 0.010% by mass is still more preferable, 0.015% by mass is still more preferable, 0.020% by mass is particularly preferable. As the upper limit of the content of the modified monomer unit, 5.0% by mass is preferable, 3.0% by mass is more preferable, 1.0% by mass is still more preferable, 0.80% by mass is still more preferable, 0.60% by mass is still more preferable, 0.50% by mass is still more preferable, 0.40% by mass is still more preferable, 0.30% by mass is still more preferable, 0.20% by mass is particularly preferable. In this specification, the above modified monomer unit means a part of the molecular structure of the TFE-based polymer and is a part derived from the modified monomer.

[0043] The content of each of the above polymerization units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis according to the type of monomer.

[0044] The above-mentioned modified monomer is not particularly limited as long as it can copolymerize with TFE. For example, perfluoroolefins such as hexafluoropropylene [HFP]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as chlorotrifluoroethylene [CTFE]; perfluorovinyl ether; perfluoroallyl ether; (perfluoroalkyl)ethylene, ethylene, monomers having a polar group, etc. may be mentioned. Further, the modified monomer to be used may be one kind or a plurality of kinds.

[0045] The above-mentioned perfluorovinyl ether is not particularly limited. For example, the following general formula (A): CF2=CF-ORf 1 (A) (In the formula, Rf 1 represents a perfluoro organic group.) Perfluoro unsaturated compounds represented by the formula and the like may be mentioned. In this specification, the above-mentioned "perfluoro organic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted by fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen.

[0046] As the above-mentioned perfluorovinyl ether, for example, in the above general formula (A), Rf 1 is a perfluoro(alkyl vinyl ether) [PAVE] in which the perfluoroalkyl group has 1 to 10 carbon atoms. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

[0047] Examples of the perfluoroalkyl group in the above-mentioned PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, and the like.

[0048] As the above-mentioned perfluorovinyl ether, further, in the above general formula (A), Rf 1is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 1 is the following formula:

[0049]

Chem.

[0050] (wherein m represents 0 or an integer of 1 to 4), Rf 1 is the following formula:

[0051]

Chem.

[0052] (wherein n represents an integer of 1 to 4), etc. are exemplified.

[0053] (Perfluoroalkyl)ethylene [PFAE] is not particularly limited, and examples thereof include (perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene, etc.

[0054] As perfluoroallyl ether, for example, the general formula (B): CF2=CF-CF2-ORf 2 (B) (wherein Rf 2 represents a perfluoro organic group). The fluoromonomer represented thereby is exemplified.

[0055] The above Rf 2A perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms is preferable. As the perfluoroallyl ether, at least one selected from the group consisting of CF2=CF-CF2-O-CF3, CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is preferable, at least one selected from the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is more preferable, and CF2=CF-CF2-O-CF2CF2CF3 is even more preferable.

[0056] The modified monomer is represented by the following general formula (i): CX 1 X 2 =CX 3 X 4 (i) (In the formula, X 1 ~X 3 are each independently H or F. X 4 is F, Cl, Rf or O-Rf. Rf is a perfluoro organic group.) is preferably a compound represented by the formula.

[0057] As Rf in the general formula (i), a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a perfluoroalkyl group having 1 to 4 carbon atoms is even more preferable.

[0058] The monomer having the polar group may be a non-fluorinated monomer or a fluorinated monomer.

[0059] Examples of the non-fluorine monomer include non-fluorine monomers having a hydroxyl group such as hydroxyalkyl vinyl ethers like hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, hydroxycyclohexyl vinyl ether; non-fluorine monomers having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, succinic acid, fumaric acid, crotonic acid, maleic acid, citraconic acid, undecylenic acid, acetylenedicarboxylic acid; non-fluorine monomers having an acid anhydride residue such as itaconic anhydride (hereinafter also referred to as "IAH"), citraconic anhydride (hereinafter also referred to as "CAH"), 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), succinic anhydride, fumaric anhydride, maleic anhydride; non-fluorine monomers having a sulfo group such as vinylsulfonic acid; non-fluorine monomers having an epoxy group (glycidyl group) such as glycidyl vinyl ether, glycidyl allyl ether; non-fluorine monomers having an amino group such as aminoalkyl vinyl ether, aminoalkyl allyl ether; non-fluorine monomers having an amide group such as (meth)acrylamide, methylolacrylamide; non-fluorine monomers having a nitrile group such as acrylonitrile, methacrylonitrile, and the like. Among these, non-fluorine monomers having a carboxyl group and non-fluorine monomers having an acid anhydride residue are preferable, non-fluorine monomers having an acid anhydride residue are more preferable, and cyclic non-fluorine monomers having an acid anhydride residue are still more preferable.

[0060] It is also preferable that the non-fluorine monomer is a monomer (10) represented by the following general formula (10). Formula (10): CH2=CR 11 -L 11 -R 12 R 11 represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 3, more preferably 1. L 11 represents a single bond, -CO-O-*, -O-CO-* or -O-. * is R 12represents the bonding position. For example, when L 11 is -CO-O-*, formula (10) is CH2=CR 11 -CO-O-R 12 is represented. R 12 represents a hydrogen atom, an alkyl group or a nitrile group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear or cyclic. When the alkyl group is cyclic, it corresponds to a cycloalkyl group.

[0061] As the monomer (10), a monomer selected from the group consisting of the monomer represented by formula (10-1), the monomer represented by formula (10-2), the monomer represented by formula (10-3), and the monomer represented by formula (10-4) is preferable. Formula (10-1) CH2=CR 11 -CO-O-R 13 Formula (10-2) CH2=CR 11 -O-CO-R 14 Formula (10-3) CH2=CR 11 -O-R 15 Formula (10-4) CH2=CR 11 -R 16 R 11 is defined as described above. R 13 represents a hydrogen atom or an alkyl group, and an alkyl group having 1 to 6 carbon atoms is preferable. R 14 represents an alkyl group, and an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. R 15 represents an alkyl group, and a linear alkyl group or a cyclic alkyl group is preferable. R 16 represents a nitrile group.

[0062] Examples of the monomer (10) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, vinyl methacrylate, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, ethyl vinyl ether, and cyclohexyl vinyl ether. As the monomer (10), the monomer represented by the formula (10-1) and the monomer represented by the formula (10-2) are more preferable. R 13 Particularly preferable is the monomer represented by the formula (10-1) in which R is an alkyl group having 1 to 6 carbon atoms.

[0063] It is also preferable that the monomer having the polar group contains a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group (hereinafter referred to as "modified monomer (A)").

[0064] Examples of the hydrophilic group in the modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 7 is H or an organic group, and may be the same or different. Any two of them may be bonded to each other to form a ring.). Among the above hydrophilic groups, -SO3M or -COOM is preferable. R 7 is preferably H or an organic group of C 1-10 is more preferably H or an organic group of C 1-4 is still more preferably H or an alkyl group of C 1-4 The metal atom includes a monovalent or divalent metal atom, such as an alkali metal (Group 1) and an alkaline earth metal (Group 2), and Na, K, or Li is preferable. Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferable.

[0065] Examples of the "functional group capable of reacting by radical polymerization" in the modified monomer (A) include groups having an ethylenically unsaturated bond such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond can be represented by the following formula: CX e X g =CX f R- (In the formula, X e , X f and X g are each independently F, Cl, H, CF3, CF2H, CFH2, or CH3; and R is a linking group.) Examples of the linking group of R include the linking group as R a described later. Preferably, groups having an unsaturated bond such as -CH=CH2, -CF=CH 2、 -CH=CF 2、 -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CH=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, -O-CF2-CF=CF2 are included.

[0066] Since the modified monomer (A) has a functional group capable of reacting by radical polymerization, when used in polymerization, it is presumed to react with the fluorine-containing monomer at the initial stage of the polymerization reaction to form particles having a hydrophilic group derived from the modified monomer (A) and high stability. Therefore, when polymerization is carried out in the presence of the modified monomer (A), it is considered that the number of particles increases.

[0067] The above-mentioned modified monomer (A) may be used alone or in combination of two or more.

[0068] As the above-mentioned modified monomer (A), a compound having an unsaturated bond can be used.

[0069] The modified monomer (A) has the general formula (4): CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4) (In the formula, X i , X j and X k are each independently F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a linking group; Z 1 and Z 2 are each independently H, F or CF3, and k is 0 or 1). A compound represented by is preferred.) Examples of the hydrophilic group include, for example, -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, R 7 is H or an organic group, and may be the same or different. Any two of them may be bonded to each other to form a ring.). Among them, -SO3M or -COOM is preferred as the hydrophilic group. As R 7 , H or a C 1-10 organic group is preferred, H or a C 1-4 organic group is more preferred, and an alkyl group of H or C 1-4 is even more preferred.) Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.) By using the modified monomer (A), an aqueous dispersion having a smaller average primary particle size and better stability can be obtained. Also, the aspect ratio of the primary particles can be made smaller.)

[0070] The above R ais a linking group. In this specification, "linking group" refers to a divalent linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or even 20 or more. The upper limit is not limited, for example, it may be 100 or less, or 50 or less. The above linking group may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and optionally contains one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate. The above linking group may not contain a carbon atom and may be a chain heteroatom such as oxygen, sulfur, or nitrogen.

[0071] The above R a is preferably, for example, a chain heteroatom such as oxygen, sulfur, nitrogen, or a divalent organic group. R a When it is a divalent organic group, the hydrogen atom bonded to the carbon atom may be replaced by a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. Also, R a may be either linear or branched, and may be either cyclic or acyclic. Also, R a may contain a functional group (for example, ester, ether, ketone, amine, halide, etc.). R a may also be a non-fluorine divalent organic group or a partially fluorinated or perfluorinated divalent organic group. R aExamples include a hydrocarbon group in which no fluorine atom is bonded to a carbon atom, a hydrocarbon group in which some of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms, a hydrocarbon group in which all of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms, -(C=O)-, -(C=O)-O-, or a hydrocarbon group containing -(C=O)-, which may contain an oxygen atom, may contain a double bond, and may contain a functional group.

[0072] R a is preferably a hydrocarbon group having 1 to 100 carbon atoms which may contain an ether bond and may contain a carbonyl group, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with fluorine. R a is preferably -(CH2) a -, -(CF2) a -, -O-(CF2) a -, -(CF2) a -O-(CF2) b -, -O(CF2) a -O-(CF2) b -, -(CF2) a -[O-(CF2) b c -, -O(CF2) a -[O-(CF2) b c -, -[(CF2) a -O] b -[(CF2) c -O] d -, -O[(CF2) a -O] b -[(CF2) c -O] d -, -O-[CF2CF(CF3)O] a -(CF2) b -, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2) a -, -(C=O)-(CF2) a -, -(C=O)-O-(CH2) a -, -(C=O)-O-(CF2) a ​​-, -(C=O)-[(CH2) a -O] b -, -(C=O)-[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -, -(C=O)-O[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -(CH2) c -, -(C=O)-O[(CF2) a -O] b -(CF2) c -, -(C=O)-(CH2) a -O-(CH2) b -, -(C=O)-(CF2) a -O-(CF2) b -, -(C=O)-O-(CH2) a -O-(CH2) b -, -(C=O)-O-(CF2) a -O-(CF2) b -, -(C=O)-O-C6H4-, and at least one selected from combinations thereof. Wherein a, b, c, and d are each independently at least 1 or more. a, b, c, and d may each independently be 2 or more, 3 or more, 4 or more, 10 or more, 20 or more. The upper limit of a, b, c, and d is, for example, 100.

[0073] R aSuitable specific examples include: -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CH2-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -, -(C=O)-[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-(CH2)2-O-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-, -(C=O)-O-C6H4-, etc. Among them, the above R a Specifically, -CF2-O-, -CF2-O-CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-O-(CH2)-, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-(CH2)2-O-(CH2)-, or -(C=O)-O-C6H4- is preferred. In the above formula, n is an integer from 1 to 10.

[0074] -R in the general formula (4) above a -(CZ 1 Z 2) k include -CF2-O-CF2-, -CF2-O-CF(CF3)-, -CF2-O-C(CF3)2-, -CF2-O-CF2-CF2-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2-C(CF3)2-, -CF2-O-CF2CF2-CF2-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF2CF2-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)CF2-CF2-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-C(CF3)2-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-C(CF3)2-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -(CH2)-, -(C=O)-[(CF2)2-O] n -(CF2)-, -(C=O)-[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-[(CF2)2-O] n -(CF2)-(CF2)-, -(C=O)-O[(CH2)2-O] n -(CF2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-O[(CF2)2-O] n-(CF2)-(CF2)-, -(C=O)-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, -(C=O)-O-(CF2)2-O-(CF2)-C(CF3)2-, or -(C=O)-O-C6H4-C(CF3)2- is preferred, and -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -(C=O)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CH2)-(CH2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, or -(C=O)-O-C6H4-C(CF3)2- is more preferred. In the above formula, n is an integer from 1 to 10.

[0075] Specific examples of the compound represented by the general formula (4) include

Chemical formula

[0076] R a As, the following general formula (r1): -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -(r1) (In the formula, X 6is independently H, F, or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1), and the divalent group represented by the following general formula (r2) is preferred: -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g -(r2) (In the formula, X 7 is independently H, F, or CF3, e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1.) The divalent group represented by this is also preferred.

[0077] For -R in the above general formula (4) a -CZ 1 Z 2 - as, there is also the following formula (t1): -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 -(t1) (In the formula, X 6 is independently H, F, or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1, and Z 1 and Z 2 are each independently F or CF3.) The divalent group represented by this is also preferred. In formula (t1), it is more preferred that Z 1 and Z 2 are such that one is F and the other is CF3. Also, in the above general formula (4), for -R a -CZ 1 Z 2 - as, there is the following formula (t2): -(C=O) h -(O) i -CF2-O-(CX 7 2)e -(O) g -CZ 1 Z 2 -(t2) (wherein X 7 is independently H, F or CF3, e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, and Z 1 and Z 2 are each independently H, F or CF3), and in formula (t2), Z 1 and Z 2 are more preferably such that one is F and the other is CF3.

[0078] The compound represented by general formula (4) preferably has a C-F bond and no C-H bond except for the hydrophilic group (Y 3 ). That is, in general formula (4), all of X i , X j , and X k are F, and R a is preferably a perfluoroalkylene group having 1 or more carbon atoms. The above perfluoroalkylene group may be linear or branched, cyclic or acyclic, and may contain at least one chain heteroatom. The number of carbon atoms of the above perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0079] The compound represented by general formula (4) may be partially fluorinated. That is, the compound represented by general formula (4) preferably has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom except for the hydrophilic group (Y 3 ).

[0080] The compound represented by general formula (4) is also preferably a compound represented by the following formula (4a). CF2=CF-O-Rf 0 -Y 3 (4a) (wherein Y 3 is a hydrophilic group and Rf 0is a perfluorinated, divalent linking group which may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and which optionally additionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.)

[0081] The compound represented by the general formula (4) is preferably a compound represented by the following formula (4b). CH2=CH-O-Rf 0 -Y 3 (4b) (In the formula, Y 3 is a hydrophilic group, and Rf 0 is a perfluorinated divalent linking group defined by formula (4a).)

[0082] In general formula (4), Y 3 is preferably one form which is -OSO3M. When Y 3 is -OSO3M, examples of the polymerization unit based on the compound represented by the general formula (4) include -[CF2CF(OCF2CF2CH2OSO3M)]-, -[CH2CH((CF2)4CH2OSO3M)]-, -[CF2CF(O(CF2)4CH2OSO3M)]-, -[CF2CF(OCF2CF(CF3)CH2OSO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CH2OSO3M)]-, -[CH2CH((CF2)4CH2OSO3M)]-, -[CF2CF(OCF2CF2SO2N(CH3) CH2CH2OSO3M)]-, -[CH2CH(CF2CF2CH2OSO3M)]-, -[CF2CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M)]-, -[CH2CH(CF2CF2CH2OSO3M)]-, etc. In the above formulas, M is the same as above.)

[0083] In general formula (4), Y 3 is preferably one form which is -SO3M. When Y 3When it is -SO3M, examples of the polymerizable unit based on the compound represented by the general formula (4) include -[CF2CF(OCF2CF2SO3M)]-, -[CF2CF(O(CF2)4SO3M)]-, -[CF2CF(OCF2CF(CF3)SO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M)]-, -[CH2CH((CF2)4SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, -[CH2CH((CF2)4SO3M)]-, etc. In the above formula, M is the same as defined above.

[0084] In the general formula (4), Y 3 being -COOM is also one of the preferred forms. Y 3 When Y is -COOM, examples of the polymerizable unit based on the compound represented by the general formula (4) include -[CF2CF(OCF2CF2COOM)]-, -[CF2CF(O(CF2)5COOM)]-, -[CF2CF(OCF2CF(CF3)COOM)]-, -[CF2CF(OCF2CF(CF3)O(CF2) n COOM)]- (n is greater than 1), -[CH2CH(CF2CF2COOM)]-, -[CH2CH((CF2)4COOM)]-, -[CH2CH(CF2CF2COOM)]-, -[CH2CH((CF2)4COOM)]-, -[CF2CF(OCF2CF2SO2NR’CH2COOM)]-, -[CF2CF(O(CF2)4SO2NR’CH2COOM)]-, -[CF2CF(OCF2CF(CF3)SO2NR’CH2COOM)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM)]-, -[CH2CH(CF2CF2SO2NR’CH2COOM)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM)]-, -[CH2CH((CF2)4SO2NR’CH2COOM)]-, -[CH2CH(CF2CF2SO2NR’CH2COOM)]-, -[CH2CH((CF2)4SO2NR’CH2COOM)]-, etc. In the above formula, R’ is H or C1-4 is an alkyl group, and M is the same as above.

[0085] In general formula (4), Y 3 being -OPO3M is also one of the preferred forms. Y 3 When Y is -OPO3M, examples of the polymerizable unit based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2CH2OP(O)(OM)2)]-, -[CF2CF(O(CF2)4CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2)]-, -[CH2CH(CF2CF2CH2OP(O)(OM)2)]-, -[CH2CH((CF2)4CH2OP(O)(OM)2)]-, -[CH2CH(CF2CF2CH2OP(O)(OM)2)]-, -[CH2CH((CF2)4CH2OP(O)(OM)2)]-, etc. In the above formulas, M is the same as above.

[0086] In general formula (4), Y 3 being -PO3M is also one of the preferred forms. Y 3 When Y is -PO3M, examples of the polymerizable unit based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2P(O)(OM)2)]-, -[CF2CF(O(CF2)4P(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)P(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2)]-, -[CH2CH(CF2CF2P(O)(OM)2)]-, -[CH2CH((CF2)4P(O)(OM)2)]-, -[CH2CH(CF2CF2P(O)(OM)2)]-, and -[CH2CH((CF2)4P(O)(OM)2)]-, and in the formula, M is the same as above.

[0087] As the compound represented by the general formula (4) above, the following general formula (5): CX2=CY(-CZ2-O-Rf-Y 3 )(5) (In the formula, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, and Z is the same or different and is -H, -F, an alkyl group or a fluorine-containing alkyl group. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. Y 3 is the same as described above.) A monomer represented by the following general formula (6): CX2=CY(-O-Rf-Y 3 )(6) (In the formula, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, and Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. Y 3 is the same as described above.) A monomer represented by the following general formula (7): CX2=CY(-Rf-Y 3 )(7) (In the formula, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, and Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. Y 3 is the same as described above.) It is preferably at least one selected from the group consisting of monomers represented by

[0088] In the general formula (5) above, X is -H or -F. Both X may be -F, or at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0089] In the general formula (5) above, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above Y, -H, -F or -CF3 is preferable, and -F is more preferable.

[0090] In the above general formula (5), Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above Z, -H, -F or -CF3 is preferable, and -F is more preferable.

[0091] In the above general formula (5), at least one of the above X, Y and Z contains a fluorine atom is preferable. For example, X may be -H, and Y and Z may be -F.

[0092] In the above general formula (5), the above Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. The number of carbon atoms of the above-mentioned fluorine-containing alkylene group is preferably 2 or more. Further, it is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less. Examples of the above-mentioned fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, and the like. The above-mentioned fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0093] The number of carbon atoms of the fluorine-containing alkylene group having the above-mentioned ether bond is preferably 3 or more. Further, it is preferably 60 or less, more preferably 30 or less, and still more preferably 12 or less. For example, the following formula:

Chemical formula

[0094] In the above general formula (5), Y 3 is -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, R 7 is H or an organic group, and they may be the same or different. Any two of them may be bonded to each other to form a ring.). R 7 is preferably H or an organic group of C 1-10 and more preferably H or an organic group of C 1-4 and still more preferably H or an alkyl group of C 1-4 . Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferable. As the above M, -H, a metal atom or -NR 7 4 is preferable, -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7 4 is more preferable, -H, -Na, -K, -Li or -NH4 is still more preferable, -Na, -K or -NH4 is still more preferable, -Na or -NH4 is particularly preferable, and -NH4 is most preferable. As the above Y 3 , -COOM or -SO3M is preferable, and -COOM is more preferable.

[0095] Examples of the monomer represented by the general formula (5) include, for example, the following formula (5a): CX h 2 = CFCF2 - O - (CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5a) (In the formula, each X h is the same and represents F or H. n5 represents 0 or an integer of 1 to 10, and Y 3 is as defined above.). A fluoroallyl ether compound represented by the formula is exemplified as a preferable one. In general formula (5a), n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1 or 2, and still more preferably 0 or 1, in terms of being able to obtain TFE-based polymer particles with a small primary particle size. The above Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and surface activity. M is preferably H or NH4 in terms of being less likely to remain as an impurity and improving the heat resistance of the resulting composition and the stretched body obtained from the composition.

[0096] The monomer represented by general formula (5) is preferably the monomer (5b) represented by the following general formula (5b). CH2=CF(-CF2-O-Rf-Y 3 )(5b) (In the formula, Rf and Y 3 are the same as above.)

[0097] Specific examples of the monomer represented by general formula (5b) include the following formula

[0098]

Chemical formula

[0099] (In the formula, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; p1 + q1 + r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, and Y 3 is the same as above. However, when both Z 3 and Z 4 are H, p1 + q1 + r1 + s1 is not 0). Examples of the monomer include, more specifically,

[0100]

Chemical formula

[0101] etc. are preferably mentioned, and among them,

[0102]

Chemical formula

[0103] is preferably.

[0104] As the monomer represented by the general formula (5b), Y in the formula (5b) 3 is preferably -COOM, and in particular, at least one selected from the group consisting of CH2 = CFCF2OCF(CF3)COOM and CH2 = CFCF2OCF(CF3)CF2OCF(CF3)COOM (where M is the same as defined above) is preferable, and CH2 = CFCF2OCF(CF3)COOM is more preferable.

[0105] The monomer represented by the general formula (5) is preferably the monomer (5c) represented by the following general formula (5c). CX 2 2 = CFCF2 - O - (CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5c) (where each X 2 is the same and represents F or H. n5 represents 0 or an integer from 1 to 10, and Y 3 is the same as defined above.)

[0106] In the above formula (5c), the above n5 is preferably 0 or an integer from 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in terms of the stability of the resulting aqueous dispersion. The above Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion, and the above M 1 is preferably H or NH4 in terms of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body. 1

[0107] Examples of the perfluorovinyl alkyl compound represented by the above formula (5c) include CH2 = CFCF2OCF(CF3)COOM 1, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM 1 (wherein M 1 is the same as defined above.) are included.

[0108] Also, as the monomer represented by the general formula (5), monomers represented by the following general formula (5d), monomers represented by the following general formula (5e), etc. are also included.

[0109] CF2=CFCF2-O-Rf-Y 3 (5d) CF2=CF-Rf-Y 3 (5e) (wherein Rf and Y 3 are the same as above)

[0110] More specifically,

Chemical formula

[0111] In the above general formula (6), X is -H or -F. Both X may be -F, or at least one of them may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0112] In the above general formula (6), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The above fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. As the above Y, -H, -F or -CF3 is preferable, and -F is more preferable.

[0113] In the general formula (6) above, it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0114] In the general formula (6) above, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. The number of carbon atoms of the fluorine-containing alkylene group is preferably 2 or more. Also, it is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0115] The monomer represented by the general formula (6) above is preferably at least one selected from the group consisting of monomers represented by the following general formulas (6a), (6b), (6c) and (6d). CF2=CF-(CF2) n1 -Y 3 (6a) (In the formula, n1 represents an integer from 1 to 10, and Y 3 represents -SO3M 1 or -COOM 1 M 1 represents H, a metal atom, NR 7 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 7 represents H or an organic group.) CF2=CF-(CF2C(CF3)F) n2 -Y 3 (6b) (In the formula, n2 represents an integer from 1 to 5, and Y 3 is the same as defined above.) CF2=CF-O-(CFX 1 ) n3 -Y 3 (6c) (In the formula, X1 represents F or CF3, n3 represents an integer from 1 to 10, and Y 3 is the same as the above definition.) CF2=CF-O-(CF2CFX 1 O) n4 -CF2CF2-Y 3 (6d) (wherein n4 represents an integer from 1 to 10, and Y 3 and X 1 are the same as the above definition.)

[0116] In the above formula (6a), the above n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. The above Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion 1 , and M 1 is preferably H or NH4 in terms of being difficult to remain as an impurity and improving the heat resistance of the resulting molded body.

[0117] Examples of the perfluorovinyl alkyl compound represented by the above formula (6a) include CF2=CFCF2COOM 1 (wherein M 1 is the same as the above definition).

[0118] In the above formula (6b), the above n2 is preferably an integer of 3 or less in terms of the stability of the resulting aqueous dispersion, and Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion 1 , and M 1 is preferably H or NH4 in terms of being difficult to remain as an impurity and improving the heat resistance of the resulting molded body.

[0119] In the above formula (6c), the above n3 is preferably an integer of 5 or less in terms of water solubility, and the above Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion 1 , and the above M 1is preferably H or NH4 in terms of improving the dispersion stability.

[0120] In the above formula (6d), the above X 1 is preferably -CF3 in terms of the stability of the aqueous dispersion, the above n4 is preferably an integer of 5 or less in terms of water solubility, and the above Y 3 is preferably -COOM 1 in terms of obtaining appropriate water solubility and the stability of the aqueous dispersion, and the above M 1 is preferably H or NH4.

[0121] Examples of the perfluorovinyl ether compound represented by the above formula (6d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM 1 (wherein M 1 represents H, NH4 or an alkali metal).

[0122] In the above general formula (7), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In the general formula (7), at least one of X and Y preferably contains a fluorine atom.

[0123] The monomer represented by the above general formula (7) is the following general formula (7a): CF2=CF-(CF2) n1 -Y 3 (7a) (wherein n1 represents an integer of 1 to 10, and Y 3 is as defined above), and at least one selected from the group consisting of monomers represented by the following general formula (7b): CF2=CF-(CF2C(CF3)F) n2 -Y 3 (7b) (wherein n2 represents an integer of 1 to 5, and Y 3 is as defined above) is preferred. The above Y 3 is preferably -SO3M 1 or -COOM 1 and M 1is H, a metal atom, NR 7 4, preferably an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium. The above R 7 represents H or an organic group.

[0124] In the above formula (7a), the above n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. The above Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion. 1 M 1 is preferably H or NH4 in that it is difficult to remain as an impurity and the heat resistance of the resulting molded article is improved. Examples of the perfluorovinylalkyl compound represented by the above formula (7a) include CF2 = CFCF2COOM 1 (wherein M 1 is as defined above).

[0125] In the above formula (7b), the above n2 is preferably an integer of 3 or less in terms of the stability of the resulting aqueous dispersion. Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion. 1 M 1 is preferably H or NH4 in that it is difficult to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0126] The modified monomer (A) is preferably at least one selected from the group consisting of compounds represented by general formula (5c), general formula (6a), general formula (6b), general formula (6c), and general formula (6d), and more preferably a compound represented by general formula (5c).

[0127] As the above-mentioned modified monomer, at least one selected from the group consisting of CTFE, HFP, perfluoro(methyl vinyl ether) [PMVE], perfluoro(propyl vinyl ether) [PPVE], PFBE, VDF, and a monomer having a polar group is preferable in terms of improving stretchability, adhesiveness, and flexibility of the binder sheet. At least one selected from the group consisting of CTFE, HFP, PMVE, and PPVE is more preferable. At least one selected from the group consisting of CTFE, HFP, and PPVE is still more preferable. At least one selected from the group consisting of PPVE and HFP is even more preferable. HFP is particularly preferable. As the above-mentioned modified monomer, a monomer having a polar group is also preferable in terms of improving dispersibility, handleability, and adhesiveness to the current collector. At least one selected from the group consisting of a non-fluorine monomer having an acid anhydride residue and the modified monomer (A) is more preferable. At least one selected from the group consisting of a cyclic non-fluorine monomer having an acid anhydride residue and a compound represented by the general formula (5c) is still more preferable. The compound represented by the general formula (5c) is even more preferable.

[0128] The above-mentioned TFE-based polymer may have a core-shell structure. Examples of the TFE-based polymer having a core-shell structure include modified PTFE containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE in the particles. Examples of such modified PTFE include PTFE described in JP-T-2005-527652.

[0129] The above-mentioned TFE-based polymer is preferably non-melt processable. In this specification, being non-melt processable means that the melt flow rate (MFR) is less than 0.25 g / 10 min, preferably less than 0.10 g / 10 min, more preferably less than 0.05 g / 10 min, and still more preferably less than 0.01 g / 10 min. The above MFR is a value obtained as the mass (g / 10 min) of the polymer flowing out per 10 minutes from a nozzle with an inner diameter of 2.095 mm and a length of 8 mm at 372 °C under a load of 5 kg using a melt indexer in accordance with ASTM D1238.

[0130] The content of the above TFE-based polymer in the TFE-based polymer composition of the present disclosure may be 95.0% by mass or more, preferably 98.0% by mass or more, more preferably 99.0% by mass or more, still more preferably 99.5% by mass or more, particularly preferably 99.9% by mass or more, and most preferably 99.95% by mass or more, based on the above TFE-based polymer composition.

[0131] The TFE-based polymer composition of the present disclosure may contain a fluorine-containing compound having a hydrophilic group.

[0132] Examples of the above hydrophilic group include -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a , -OCOM a , and -OM a (wherein M a is -H, a metal atom, -NR 1 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and R 1 is H or an organic group). At least one selected from the group consisting of these is included. The above hydrophilic group may be an ionic group, and is preferably an anionic group.

[0133] Examples of the fluorine-containing compound having the above hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 g / mol or less. The molecular weight of the above fluorine-containing compound is preferably 800 or less, and more preferably 500 or less. In the polymer particles obtained by polymerization carried out in the presence of a fluorine-containing surfactant, in addition to the TFE-based polymer, it is normal for the fluorine-containing surfactant to be contained. In this specification, the fluorine-containing surfactant is the one used during polymerization. The fluorine-containing compound having a molecular weight of 1000 or less may be a compound that is not added during polymerization, for example, a compound that is by-produced during the polymerization. In addition, when the fluorine-containing compound having a molecular weight of 1000 or less contains an anionic part and a cationic part, it means a fluorine-containing compound in which the molecular weight of the anionic part is 1000 or less. It is assumed that the TFE-based polymer is not included in the fluorine-containing compound having a molecular weight of 1000 or less.

[0134] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include surfactants containing fluorine (anionic fluorine-containing surfactants) in which the molecular weight of the anionic part is 1000 or less. The above-mentioned "anionic part" means the part excluding the cation of the above-mentioned fluorine-containing surfactant. For example, in the case of F(CF2) n1 COOM, it is the part of "F(CF2) n1 COO".

[0135] Examples of the above-mentioned anionic fluorine-containing surfactant include the general formula (N 0 ): X n0 -Rf n0 -Y 0 (N 0 ) (In the formula, X n0 is H, Cl or F. Rf n0 is an alkylene group having 3 to 20 carbon atoms, which is linear, branched or cyclic, and in which some or all of the H are substituted by F. The alkylene group may contain one or more ether bonds, and some of the H may be substituted by Cl. Y 0 is an anionic group.) Compounds represented by the formula are included.

[0136] Y 0The anionic group may be -COOM, -SO2M, or -SO3M, and may be -COOM or -SO3M. M is H, a metal atom, NR 7 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 7 is H or an organic group. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., for example, Na, K or Li. R 7 may be H or an organic group of C 1-10 and may be H or an organic group of C 1-4 and may be H or an alkyl group of C 1-4 M may be H, a metal atom or NR 7 4, may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4, and may be H, Na, K, Li or NH4. The above Rf n0 may be one in which 50% or more of H is substituted with fluorine.

[0137] Examples of the compound represented by the general formula (N 0 ) include the general formula (N 1 ): X n0 -(CF2) m1 -Y 0 (N 1 ) (wherein X n0 is H, Cl and F, m1 is an integer of 3 to 15, and Y 0 is as defined above.) The compound represented by, the general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 ) (wherein Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, X n1 is F or CF3, and Y 0is as defined above. A compound represented by the general formula (N 3 ): Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 ) (In the formula, Rf n2 is a partially or fully fluorinated alkyl group that may contain an ether bond with 1 to 13 carbon atoms, m3 is an integer from 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group with 1 to 3 carbon atoms, q is 0 or 1, and Y 0 is as defined above. A compound represented by the general formula (N 4 ): Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 ) (In the formula, Rf n4 is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond and / or a chlorine atom with 1 to 12 carbon atoms, Y n1 and Y n2 are the same or different and are H or F, p is 0 or 1, and Y 0 is as defined above. A compound represented by the general formula (N 5 ): [Chemical formula] (In the formula, X n2 , X n3 and X n4 may be the same or different and are H, F, or a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond with 1 to 6 carbon atoms. Rf n5 is a linear or branched partially or fully fluorinated alkylene group that may contain an ether bond with 1 to 3 carbon atoms, L is a linking group, and Y 0 is as defined above. However, Xn2 and X n3 and X n4 and Rf n5 The total carbon number of is 18 or less. Compounds represented by etc. are exemplified.

[0138] As the compound represented by the general formula (N 0 ), more specifically, perfluorocarboxylic acid (I) represented by the general formula (I), ω-H perfluorocarboxylic acid (II) represented by the general formula (II), perfluoroether carboxylic acid (III) represented by the general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by the general formula (V), perfluoroalkylsulfonic acid (VI) represented by the general formula (VI), ω-H perfluorosulfonic acid (VII) represented by the general formula (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by the general formula (VIII), alkylalkylene carboxylic acid (IX) represented by the general formula (IX), fluorocarboxylic acid (X) represented by the general formula (X), alkoxyfluorosulfonic acid (XI) represented by the general formula (XI), compound (XII) represented by the general formula (XII), compound (XIII) represented by the following general formula (XIII), etc. are exemplified.

[0139] The above perfluorocarboxylic acid (I) has the general formula (I): F(CF2) n1 COOM (I) (In the formula, n1 is an integer of 3 to 14, and M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 7 is H or an organic group.) It is represented by.

[0140] The above ω-H perfluorocarboxylic acid (II) has the general formula (II): H(CF2) n2 COOM (II) It is represented by (wherein, n2 is an integer of 4 to 15, and M is as defined above).

[0141] The above perfluoroether carboxylic acid (III) is represented by the general formula (III): Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III) (wherein, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above).

[0142] The above perfluoroalkyl alkylene carboxylic acid (IV) is represented by the general formula (IV): Rf 2 (CH2) n4 Rf 3 COOM (IV) (wherein, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above).

[0143] The above alkoxyfluorocarboxylic acid (V) is represented by the general formula (V): Rf 4 -O-CY 1 Y 2 CF2-COOM (V) (wherein, Rf 4 is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond and / or a chlorine atom having 1 to 12 carbon atoms, Y 1 and Y 2 are the same or different and are H or F, and M is as defined above).

[0144] The above perfluoroalkyl sulfonic acid (VI) is represented by the general formula (VI): F(CF2) n5SO3M (VI) (wherein n5 is an integer of 3 to 14, and M is as defined above).

[0145] The above ω-H perfluorosulfonic acid (VII) has the general formula (VII): H(CF2) n6 SO3M (VII) (wherein n6 is an integer of 4 to 14, and M is as defined above).

[0146] The above perfluoroalkylalkylene sulfonic acid (VIII) has the general formula (VIII): Rf 5 (CH2) n7 SO3M (VIII) (wherein Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above).

[0147] The above alkylalkylene carboxylic acid (IX) has the general formula (IX): Rf 6 (CH2) n8 COOM (IX) (wherein Rf 6 is a linear or branched or fully fluorinated alkyl group which may contain an ether bond having 1 to 13 carbon atoms, n8 is an integer of 1 to 3, and M is as defined above).

[0148] The above fluorocarboxylic acid (X) has the general formula (X): Rf 7 -O-Rf 8 -O-CF2-COOM (X) (wherein Rf 7 is a linear or branched or fully fluorinated alkyl group which may contain an ether bond and / or a chlorine atom having 1 to 6 carbon atoms, Rf 8is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above.) is represented by

[0149] The above alkoxyfluorosulfonic acid (XI) has the general formula (XI): Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI) (In the formula, Rf 9 is a linear or branched, partially or fully fluorinated alkyl group which may contain an ether bond having 1 to 12 carbon atoms and may contain chlorine, Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.) is represented by

[0150] The above compound (XII) has the general formula (XII):

Chemical formula

[0151] The above compound (XIII) has the following general formula (XIII): Rf 11 -O-(CF2CF(CF3)O) n9(CF2O) n10 CF2COOM (XIII) (wherein, Rf 11 is a fluoroalkyl group having 1 to 5 carbon atoms and containing chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above.) It is represented by. As the compound (XIII), CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10 CF2COONH4 (a mixture with an average molecular weight of 750, wherein n9 and n10 are as defined above.) can be mentioned.

[0152] Thus, examples of the anionic fluorine-containing surfactant include carboxylic acid surfactants and sulfonic acid surfactants.

[0153] The fluorine-containing surfactant may be a single fluorine-containing surfactant or a mixture containing two or more fluorine-containing surfactants.

[0154] Examples of the fluorine-containing surfactant include compounds represented by the following formulas. The fluorine-containing surfactant may be a mixture of these compounds. F(CF2)7COOM, F(CF2)5COOM, H(CF2)6COOM, H(CF2)7COOM, CF3O(CF2)3OCHFCF2COOM, C3F7OCF(CF3)CF2OCF(CF3)COOM, CF3CF2CF2OCF(CF3)COOM, CF3CF2OCF2CF2OCF2COOM, C2F5OCF(CF3)CF2OCF(CF3)COOM, CF3OCF(CF3)CF2OCF(CF3)COOM, CF2ClCF2CF2OCF(CF3)CF2OCF2COOM, CF2ClCF2CF2OCF2CF(CF3)OCF2COOM, CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM, CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, and, [Chemical formula] (In each formula, M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent. R 7 is H or an organic group.).

[0155] In the above formulas, M may be H, a metal atom or NR 7 4, may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4, may be H, Na, K, Li or NH4. R 7 may be H or an organic group of C 1-10 may be H or an organic group of C 1-4 may be H or an organic group of C 1-4 and may be an alkyl group.

[0156] The content of the above anionic fluorine-containing surfactant is preferably 25 mass ppb or less, more preferably 20 mass ppb or less, still more preferably 15 mass ppb or less, still more preferably 10 mass ppb or less, still more preferably less than 10 mass ppb, still more preferably 1 mass ppb or less, still more preferably less than 1 mass ppb, and particularly preferably less than the quantification lower limit. The lower limit is not particularly limited and may be an amount less than the quantification lower limit.

[0157] The amount of the above anionic fluorine-containing surfactant is measured by the following method. Weigh 1 g of the sample, add 10 g (12.6 ml) of methanol, perform ultrasonic treatment for 60 minutes to obtain an extract. Appropriately concentrate the obtained extract by nitrogen purging, and measure the fluorine-containing compound in the concentrated extract by LC / MS / MS. Extract the molecular weight information from the obtained LC / MS spectrum and confirm the match with the structural formula of the candidate fluorine-containing compound. Prepare aqueous solutions of five or more levels of the standard substance, perform LC / MS analysis on the aqueous solutions of each content, plot the relationship between the content and the area of the corresponding area, and draw a calibration curve. Using the above calibration curve, convert the area of the LC / MS chromatogram of the fluorine-containing compound in the extract into the content of the fluorine-containing compound. Note that the lower limit of quantification in this measurement method is 10 mass ppb.

[0158] The TFE-based polymer composition containing an anionic fluorine-containing surfactant can be obtained, for example, by polymerization using an anionic fluorine-containing surfactant.

[0159] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include compounds represented by the following general formula (1) (hereinafter also referred to as compound (1)). General formula (1): (H-(CF2) m-1 -COO) p M 1 (In the formula, m is 4 to 20. M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.)

[0160] M 1 Examples of the metal atom as M include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. The four Rs 5 may be the same or different. R5 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0161] In the general formula (1), m is preferably 6 or more, more preferably 8 or more, still more preferably 11 or more, still more preferably 13 or more, particularly preferably 15 or more, and preferably 18 or less, more preferably 16 or less.

[0162] The TFE-based polymer composition of the present disclosure may contain one or more of the compound (1), or may contain two or more, or may contain three or more.

[0163] The content of the compound (1) (when two or more are present, the content for each component) may be 10 mass ppm or less, preferably 5000 mass ppb or less, more preferably 1000 mass ppb or less, still more preferably 500 mass ppb or less, still more preferably 100 mass ppb or less, still more preferably 50 mass ppb or less, still more preferably 25 mass ppb or less, particularly preferably 10 mass ppb or less with respect to the above TFE-based polymer. The lower limit is not particularly limited, but may be 0.1 mass ppb or may be 1 mass ppb.

[0164] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include a compound represented by the following general formula (2) (hereinafter also referred to as compound (2)). General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is the same as above), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.)

[0165] M 2 Examples of the metal atom as M include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. Four Rs 5 may be the same or different. R 5 is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms.

[0166] In the general formula (2), n is preferably 6 or more, more preferably 8 or more, still more preferably 11 or more, still more preferably 13 or more, particularly preferably 15 or more, and preferably 18 or less, more preferably 16 or less.

[0167] The TFE-based polymer composition of the present disclosure may contain one or more compounds (2), or may contain two or more compounds (2), or may contain three or more compounds (2).

[0168] The content of the compound (2) (when two or more are present, the content for each component) may be 10 mass ppm or less, preferably 5000 mass ppb or less, more preferably 1000 mass ppb or less, still more preferably 500 mass ppb or less, still more preferably 100 mass ppb or less, still more preferably 50 mass ppb or less, still more preferably 25 mass ppb or less, still more preferably 10 mass ppb or less, still more preferably 1 mass ppb or less, still more preferably less than 1 mass ppb, and particularly preferably less than the quantification limit. The lower limit is not particularly limited and may be an amount less than the quantification limit.

[0169] The TFE-based polymer composition containing compound (1) and / or (2) is obtained by using a hydrocarbon surfactant. The TFE-based polymer composition of the present disclosure may contain a hydrocarbon surfactant together with the TFE-based polymer and compound (1) and / or (2). The content of the hydrocarbon surfactant in the above TFE-based polymer composition is not particularly limited, but is usually 100 mass ppm to 10 mass%. It is preferable that in the above hydrocarbon surfactant, the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0170] The TFE-based polymer composition of the present disclosure preferably does not substantially contain a compound represented by the following general formula (3) (hereinafter also referred to as compound (3)). General formula (3): (H-(CF2)8-SO3) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.)

[0171] Not substantially containing compound (3) means that the content of compound (3) is 25 mass ppb or less with respect to the above TFE-based polymer. The content of compound (3) is preferably 20 mass ppb or less, more preferably 15 mass ppb or less, still more preferably 10 mass ppb or less with respect to the above TFE-based polymer. The lower limit is not particularly limited, and may be 0 mass ppb, may be 0.1 mass ppb, or may be 1 mass ppb.

[0172] The contents of the compounds (1), (2) and (3) are the values measured by liquid chromatography mass spectrometry as described in the examples described later.

[0173] Examples of the fluorine-containing compound having the above hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000 g / mol.

[0174] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000 include, for example, a polymer compound having an ionic group. It should be noted that the above TFE-based polymer is not included in the above polymer compound.

[0175] As the above ionic group, an anionic group is preferable. For example, a sulfate group, -COOM a (carboxylate group), a phosphate group, -PO3M a (phosphonate group), -SO3M a (sulfonate group), -SO2M a (sulfinate group), -C(CF3)2OM a (In each formula, M a is -H, a metal atom, -NR 2 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 2 is H or an organic group.) and the like can be mentioned. Among them, at least one selected from the group consisting of -SO3M a , -SO2M a , -PO3M a and -COOM a is preferable.

[0176] The content of the ionic group is preferably 0.80 meq / g or more, more preferably 1.20 meq / g or more, still more preferably 1.75 meq / g or more, even more preferably 2.00 meq / g or more, and particularly preferably 2.50 meq / g or more, based on the above polymer compound. The content may also be 10.0 meq / g or less, may be 8.00 meq / g or less, or may be 5.00 meq / g or less. The content of the ionic group is determined by calculation from the composition of the above polymer compound.

[0177] The above polymer compound preferably contains fluorine atoms, and preferably the ratio of hydrogen atoms bonded to carbon atoms in the polymer compound replaced by fluorine atoms is 50% or more. The "ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms" is determined as the ratio of the number of fluorine atoms to the total number of hydrogen atoms bonded to carbon atoms and halogen atoms (including fluorine atoms) bonded to carbon atoms. The ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms in the above polymer compound is not particularly limited, but is more preferably 70% or more, still more preferably 80% or more, even more preferably 90% or more, particularly preferably 95% or more, and most preferably 100%.

[0178] The above polymer compound preferably has an ion exchange ratio (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the main chain of the above polymer compound relative to the ionic group. A precursor group that becomes ionic by hydrolysis (for example, -SO2F) is not regarded as an ionic group for the purpose of determining the IXR. The above IXR is preferably 0.5 or more, more preferably 1 or more, still more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. Also, the IXR is preferably 43 or less, more preferably 33 or less, and still more preferably 23 or less. In the above polymer compound, the ionic groups are typically distributed along the polymer main chain. The above polymer compound includes repeating side chains bonded to the polymer main chain, and these side chains preferably have ionic groups.

[0179] The above polymer compound is preferably a water-soluble polymer compound. "Water-soluble" means the property of being easily dissolved or dispersed in an aqueous medium. A polymer compound having water solubility can have its particle size measured by, for example, the dynamic light scattering method (DLS) and show a particle size that cannot be measured or is 5 nm or less. On the other hand, a polymer compound having water insolubility can have its particle size measured by, for example, the dynamic light scattering method (DLS) and show a particle size greater than 5 nm.

[0180] The number average molecular weight of the above polymer compound is preferably greater than 0.1×10 4 more preferably greater than 0.15×10 4 even more preferably greater than 0.2×10 4 even more preferably greater than 0.3×10 4 even more preferably greater than 0.5×10 4 even more preferably greater than 1.0×10 4 even more preferably greater than 2.0×10 4 even more preferably greater than 3.0×10 4 most preferably greater than 3.0×10 4 and preferably less than 75.0×10 4 more preferably less than 50.0×10 4 even more preferably less than 40.0×10 4 even more preferably less than 30.0×10 4 even more preferably less than 20.0×10

[0181] The weight average molecular weight of the above polymer compound is preferably greater than 0.1×10 4 more preferably greater than 0.2×10 4 even more preferably greater than 0.4×10 4 even more preferably greater than 0.6×10 4 even more preferably greater than 1.0×10 4 even more preferably greater than 2.0×10 4The above is particularly preferred, 5.0×10 4 The above is most preferred. Also, 150.0×10 4 The following is preferred, 100.0×10 4 The following is more preferred, 80.0×10 4 The following is even more preferred, 60.0×10 4 The following is even more preferably, 40.0×10 4 The following is particularly preferred.

[0182] The above number average molecular weight and weight average molecular weight are values calculated by gel permeation chromatography (GPC) using monodisperse polystyrene, or monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) as standards for the molecular weight. Also, when measurement by GPC is not possible, the number average molecular weight of the above polymer compound can be determined by the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0183] It is preferable that the above polymer compound substantially does not contain a fraction with a molecular weight of 1000 or less, more preferably substantially does not contain a fraction with a molecular weight of less than 1500, even more preferably substantially does not contain a fraction with a molecular weight of less than 2000, and particularly preferably substantially does not contain a fraction with a molecular weight of less than 3000. Substantially not containing the above fraction means that the content of the above fraction in the above polymer compound is 3.0% by mass or less. The content of the above fraction is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less with respect to the above polymer compound. The content of the above fraction can be measured by gel permeation chromatography (GPC) or liquid chromatography-mass spectrometry (LC-MS).

[0184] The above-mentioned polymer compound preferably substantially does not contain a fluorine-containing compound having a molecular weight of 1000 or less. Substantially not containing the fluorine-containing compound means that the amount of the fluorine-containing compound is 25 mass ppb or less with respect to the polymer compound. More preferably, the amount of the fluorine-containing compound is less than 25 mass ppb, still more preferably 10 mass ppb or less, still more preferably less than 10 mass ppb, still more preferably 5 mass ppb or less, still more preferably 3 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably less than 1 mass ppb. The lower limit is not particularly limited and may be an amount less than the detection limit. The fluorine-containing compound having a molecular weight of 1000 or less and its quantification method will be described later.

[0185] The above-mentioned polymer compound is preferably at least one selected from the group consisting of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II). General formula (I): CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; A 0 is an anionic group; X 2 is H, F, an alkyl group or a fluorine-containing alkyl group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluorine-containing alkyl group; m is an integer of 1 or more.) General formula (II): T X -X A -R FA1 -R FA2 -X A -T X’ (II) (wherein R FA1 is -Rf 1 p -R F -O q - and R FA2 is -Rf 2 p -R FX -O q - and R F is a divalent fluoropolyether group R FX is a divalent fluoropolyether group containing an anionic group Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms p is each independently 0 or 1 q is each independently 0 or 1 X A are each independently a single bond or a group having a valence of 2 to 10 T X and T X ’ are each independently (i) a C1 - C 24 (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and does not have the above anionic group, and (ii) a C1 - C 24 (hydro)(fluoro)carbon group containing at least one of the above anionic groups, and are selected from the group consisting of.)

[0186] Polymer (I) is a polymer containing a polymerization unit (I) based on monomer (I). Monomer (I) is represented by the following general formula (I). CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (wherein X 1 and X 3is independently F, Cl, H, or CF3; X 2 is H, F, an alkyl group, or a fluorinated alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more.) X 2 is preferably F, Cl, H, or CF3. Also, Z 1 and Z 2 are preferably F or CF3.

[0187] In the present disclosure, the anionic group includes, in addition to anionic groups such as a sulfate group and a carboxylate group, functional groups that give anionic groups such as an acid group like -COOH and an acid salt group like -COONH4. Preferred anionic groups include a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group, a sulfinate group, or -C(CF3)2OM a (wherein M a is -H, a metal atom, -NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 2 is H or an organic group.)

[0188] In the present disclosure, as the monomer (I) represented by the general formula (I), one or two or more monomers can be used.

[0189] R is a linking group. In the present disclosure, the "linking group" is a (m + 1)-valent linking group, and when m is 1, it is a divalent linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. The upper limit is not limited, but may be, for example, 100 or less or 50 or less.

[0190] The linking group may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and may optionally contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may optionally contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate. The linking group may not contain a carbon atom and may be a chain heteroatom such as oxygen, sulfur, or nitrogen.

[0191] m is an integer of 1 or more, preferably 1 or 2, more preferably 1. When m is an integer of 2 or more, Z 1 , Z 2 and A 0 may be the same or different. Next, a preferred configuration when m is 1 in the general formula (I) will be described.

[0192] R is preferably a chain heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0193] The polymer (I) is also preferably highly fluorinated. For example, excluding anionic groups (A a ) such as phosphate group moieties (e.g., CH2OP(O)(OM a )2) and sulfate group moieties (e.g., CH2OS(O)2OM 0 ), it is preferable that 80% or more, 90% or more, 95% or more, or 100% of the C-H bonds in the polymer (I) are replaced with C-F bonds.

[0194] The monomer (I) and the polymer (I) preferably have C-F bonds and no C-H bonds except for the anionic group (A 0 ). That is, in the general formula (I), X 1 , X 2 , and X 3All of them are F, and R is preferably a perfluoroalkylene group having 1 or more carbon atoms. The perfluoroalkylene group may be either linear or branched, either cyclic or acyclic, and may contain at least one catenary heteroatom. The number of carbon atoms in the perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0195] The monomer (I) and the polymer (I) may be partially fluorinated. That is, the monomer (I) and the polymer (I) preferably have at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom, except for the anionic group (A 0 ).

[0196] The anionic group (A 0 ) is -SO3M a , -OSO3M a , -SO2M a , -COOM a , -SO2NR’CH2COOM a , -CH2OP(O)(OM a )2, [-CH2O]2P(O)(OM a ), -CH2CH2OP(O)(OM a )2, [-CH2CH2O]2P(O)(OM a ), -CH2CH2OSO3M a , -P(O)(OM a )2, -SO2NR’CH2CH2OP(O)(OM a )2, [-SO2NR’CH2CH2O]2P(O)(OM a ), -CH2OSO3M a , -SO2NR’CH2CH2OSO3M a , or -C(CF3)2OM a . Among them, -SO3M a , -OSO3M a , -COOM a , -P(O)(OM a )2 or C(CF3)2OM a is preferable, and -COOM a , -SO3M a, -OSO3M a or C(CF3)2OM a is more preferable, -SO3M a , -COOM a or P(O)(OM a )2 is even more preferable, -SO3M a or COOM a is particularly preferable, -COOM a is most preferable.

[0197] M a is H, a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group.

[0198] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferable.

[0199] M a is preferably -H, a metal atom or NR 2 4, more preferably -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 2 4, even more preferably -H, -Na, -K, -Li or NH4, even more preferably -H, -Na, -K or NH4, particularly preferably -H, -Na or NH4, and most preferably -H or NH4.

[0200] In the polymer (I), each polymer unit (I) may have different anionic groups or the same anionic groups.

[0201] The monomer (I) is preferably a monomer represented by the general formula (Ia). The polymer (I) is preferably a polymer containing a polymer unit (Ia) based on the monomer represented by the general formula (Ia). CF2=CF-O-Rf 0 -A 0 (Ia) (In the formula, A 0is an anionic group, and Rf 0 is perfluorinated and may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and optionally additionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen. It is a perfluorinated divalent linking group.)

[0202] It is also preferable that the monomer (I) is a monomer represented by the general formula (Ib). It is also preferable that the polymer (I) is a polymer containing a polymerization unit (Ib) based on the monomer represented by the general formula (Ib). CH2=CH-O-Rf 0 -A 0 (Ib) (In the formula, A 0 is an anionic group, and Rf 0 is the perfluorinated divalent linking group defined by formula Ia.)

[0203] In the general formula (I), A 0 is preferably one form that is a sulfate group. A 0 is, for example, -CH2OSO3M a , -CH2CH2OSO3M a , or -SO2NR’CH2CH2OSO3M a , where R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.)

[0204] A 0 When A a is a sulfate group, examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2CH2OSO3M a ), CH2=CH(O(CF2)4CH2OSO3M a ), CF2=CF(O(CF2)4CH2OSO3M a ), CF2=CF(OCF2CF(CF3)CH2OSO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M a)、CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M a )、CH2=CH(OCF2CF2CH2OSO3M a )、CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M a )、CH2=CH(OCF2CF2CF2CH2OSO3M a ) etc. are included. In the above formula, M a is the same as above.

[0205] In general formula (I), it is also a preferred form that A 0 is a sulfonate group. As A 0 , for example, it is -SO3M a , and in the formula, M a is the same as above.

[0206] When A 0 is a sulfonate group, examples of the monomer represented by general formula (I) include CF2=CF(OCF2CF2SO3M a ), CF2=CF(O(CF2)3SO3M a ), CF2=CF(O(CF2)4SO3M a ), CF2=CF(OCF2CF(CF3)SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M a ), CH2=CH(OCF2CF2SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M a ), CH2=CH(O(CF2)4SO3M a ), CH2=CH(O(CF2)3SO3M a ) etc. are included. In the above formula, M a is the same as above.

[0207] In general formula (I), it is also a preferred form that A 0 is a sulfinate group. As A 0 , for example, it is -SO2M a , and in the formula, M a is the same as above.

[0208] A 0 is a sulfinate group, and examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2SO2M a ), CF2=CF(O(CF2)3SO2M a ), CF2=CF(O(CF2)4SO2M a ), CF2=CF(OCF2CF(CF3)SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO2M a ), CH2=CH(OCF2CF2SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2M a ), CH2=CH(O(CF2)4SO2M a ), CH2=CH(O(CF2)3SO2M a ), etc. In the above formula, M a is the same as above.

[0209] In the general formula (I), it is also a preferred form that A 0 is a carboxylate group. Examples of A 0 include, for example, COOM a or SO2NR’CH2COOM a , where R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above. When A 0 is a carboxylate group, examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2COOM a ), CF2=CF(O(CF2)3COOM a ), CF2=CF(O(CF2)4COOM a ), CF2=CF(O(CF2)5COOM a ), CF2=CF(OCF2CF(CF3)COOM a ), CF2=CF(OCF2CF(CF3)O(CF2) n COOM a )(n is greater than 1), CH2=CH(OCF2CF2COOM a ), CH2=CH(O(CF2)4COOMa ), CH2=CH(O(CF2)3COOM a ), CF2=CF(OCF2CF2SO2NR’CH2COOM a ), CF2=CF(O(CF2)4SO2NR’CH2COOM a ), CF2=CF(OCF2CF(CF3)SO2NR’CH2COOM a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM a ), CH2=CH(OCF2CF2SO2NR’CH2COOM a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM a ), CH2=CH(O(CF2)4SO2NR’CH2COOM a ), CH2=CH(O(CF2)3SO2NR’CH2COOM a ), etc. In the above formula, R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0210] In general formula (I), it is also a preferred form that A 0 is a phosphate group. Examples of A 0 include, for example, -CH2OP(O)(OM a )2, [-CH2O]2P(O)(OM a ), -CH2CH2OP(O)(OM a )2, [-CH2CH2O]2P(O)(OM a ), [-SO2NR’CH2CH2O]2P(O)(OM a ) or SO2NR’CH2CH2OP(O)(OM a )2, where R’ in the formula is an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0211] When A 0 is phosphate, examples of the monomer represented by general formula (I) include CF2=CF(OCF2CF2CH2OP(O)(OM a )2), CF2=CF(O(CF2)4CH2OP(O)(OM a)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CH2=CH(OCF2CF2CH2OP(O)(OM a )2), CH2=CH(O(CF2)4CH2OP(O)(OM a )2), CH2=CH(O(CF2)3CH2OP(O)(OM a )2), etc. In the above formula, M a is the same as above.

[0212] In general formula (I), it is also a preferred form that A 0 is a phosphonate group. When A 0 is a phosphonate group, as the monomer represented by general formula (I), there are CF2=CF(OCF2CF2P(O)(OM a )2), CF2=CF(O(CF2)4P(O)(OM a )2), CF2=CF(OCF2CF(CF3)P(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM a )2), CH2=CH(OCF2CF2P(O)(OM a )2), CH2=CH(O(CF2)4P(O)(OM a )2), CH2=CH(O(CF2)3P(O)(OM a )2). In the formula, M a is the same as above.

[0213] Monomer (I) is preferably the monomer (1) represented by general formula (1). Polymer (I) is preferably a polymer (1) containing a polymerization unit (1) based on the monomer represented by general formula (1). CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X is the same or different and is -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, and Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a is -H, a metal atom, -NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group.) However, at least one of X, Y and Z contains a fluorine atom.)

[0214] In the production method of the present disclosure, the monomer (1) represented by the general formula (1) may be copolymerized with another monomer. The polymer (1) may be a homopolymer of the monomer (1) represented by the general formula (1), or a copolymer with another monomer.

[0215] The fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms does not contain a structure in which an oxygen atom is at the terminal, and is an alkylene group containing an ether bond between carbon-carbon atoms.

[0216] In the general formula (1), X is -H or F. Both X may be -F, or at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0217] In general formula (1), Y is -H, -F, an alkyl group or a fluorinated alkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The above fluorinated alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. As the above Y, -H, -F or CF3 is preferable, and -F is more preferable.

[0218] In general formula (1), Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The above fluorinated alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. As the above Z, -H, -F or CF3 is preferable, and -F is more preferable.

[0219] In general formula (1), at least one of X, Y and Z contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0220] In general formula (1), the above Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms.

[0221] The number of carbon atoms in the above fluorine-containing alkylene group is preferably 2 or more. Also, the number of carbon atoms in the above fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. Examples of the above fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CF2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The above fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0222] The number of carbon atoms in the fluorine-containing alkylene group having the above ether bond is preferably 3 or more. Also, the number of carbon atoms in the fluorine-containing alkylene group having the above ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorine-containing alkylene group having the above ether bond is, for example, represented by the general formula:

Chemical formula

[0223] Specific examples of the fluorine-containing alkylene group having the above ether bond include -CF2CF(CF3)OCF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n-CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. are exemplified. The fluorine-containing alkylene group having the ether bond is preferably a perfluoroalkylene group.)

[0224] In the general formula (1), A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a is H, a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group).

[0225] R 2 is preferably H or an organic group of C 1-10 , more preferably H or an organic group of C 1-4 , and even more preferably H or an alkyl group of C 1-4 .

[0226] Examples of the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.

[0227] M a is preferably H, a metal atom or NR 2 4, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 2 4, even more preferably H, Na, K, Li or NH4, even more preferably H, Na, K or NH4, particularly preferably H, Na or NH4, and most preferably H or NH4.

[0228] A is -COOM a or SO3M a is preferred, and -COOM a is more preferred.

[0229] Examples of the monomer represented by the general formula (1) include, for example, the general formula (1a): CX2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-A (1a) (In the formula, each X is the same and represents F or H. n5 represents 0 or an integer from 1 to 10, and A is the same as defined above.) Monomers represented by this formula are exemplified.

[0230] In the general formula (1a), n5 is preferably 0 or an integer from 1 to 5, more preferably 0, 1, or 2, and even more preferably 0 or 1, in terms of being able to obtain particles with a small primary particle diameter.

[0231] In the production method of the present disclosure, the monomer represented by the general formula (1a) and another monomer may be copolymerized. The polymer (1) may be a homopolymer of the monomer represented by the general formula (1a) or a copolymer with another monomer.

[0232] The monomer (1) is preferably a monomer represented by the general formula (1A). The polymerization unit (1) is preferably a polymerization unit (1A) based on the monomer represented by the general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)

[0233] In the production method of the present disclosure, the monomer represented by the general formula (1A) and another monomer may be copolymerized. The polymer (1) may be a homopolymer of the monomer represented by the general formula (1A) or a copolymer with another monomer.

[0234] Specific examples of the monomer represented by the formula (1A) include the general formula [Chemical formula] (wherein, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; p1 + q1 + r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, provided that when Z 3 and Z 4 are both H, p1 + q1 + r1 + s1 is not 0; A is the same as defined above), and monomers represented thereby are included. More specifically, [Chemical formula] etc. are preferably included, and among them [Chemical formula] is preferably the case.

[0235] As the monomer represented by the general formula (1A), it is preferable that A in the formula (1A) is -COOM a , and in particular, CH2 = CFCF2OCF(CF3)COOM a , and CH2 = CFCF2OCF(CF3)CF2OCF(CF3)COOM a (wherein, M a is the same as defined above.) At least one selected from the group consisting of is preferable, and CH2 = CFCF2OCF(CF3)COOM a is more preferable.

[0236] Also, as the monomer represented by the general formula (1), monomers represented by the following formula etc. are also included. CF2 = CFCF2 - O - Rf - A (wherein, Rf and A are the same as above)

[0237] More specifically, [Chemical formula] etc. are included.

[0238] It is also preferable that the monomer (I) is the monomer (2) represented by the general formula (2). It is also preferable that the polymer (I) is the polymer (2) containing the polymerization unit (2) based on the monomer represented by the general formula (2). CX2=CY(-O-Rf-A) (2) (In the formula, X is the same or different and is -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond or a keto group having 2 to 100 carbon atoms. A is the same as described above.)

[0239] In the production method of the present disclosure, the monomer (2) represented by the general formula (2) and other monomers may be copolymerized. The polymer (2) may be a homopolymer of the monomer represented by the general formula (2) or a copolymer with other monomers.

[0240] In the general formula (2), X is -H or F. Both X may be -F, or at least one of them may be -H. For example, one of them may be -F and the other may be -H, or both may be -H.

[0241] In the general formula (2), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom and may have 1 or more carbon atoms. The carbon number of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom and may have 1 or more carbon atoms. The carbon number of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As Y, -H, -F or CF3 is preferable, and -F is more preferable.

[0242] In the general formula (2), it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0243] In general formula (2), the above Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms, or a fluorine-containing alkylene group having a keto group and having 2 to 100 carbon atoms. Note that the fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms does not include a structure in which an oxygen atom is at the terminal, and is an alkylene group containing an ether bond between carbon atoms.

[0244] The number of carbon atoms of the fluorine-containing alkylene group of Rf is preferably 2 or more. Further, it is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, -CF2CF2CF2-, CF2CF2CF2CF2-, etc. The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0245] The number of carbon atoms of the fluorine-containing alkylene group having the above ether bond is preferably 3 or more. Further, the number of carbon atoms of the fluorine-containing alkylene group having the above ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, and particularly preferably 5 or less. The fluorine-containing alkylene group having the above ether bond is, for example, represented by the general formula:

Chemical formula

[0246] Specific examples of the fluorine-containing alkylene group having the ether bond include -CF2CF(CF3)OCF2CF2-, -CF2CF(CF3)OCF2CF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(wherein n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n -CF(CF3)CH2-(wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, and the like. The fluorine-containing alkylene group having the ether bond is preferably a perfluoroalkylene group.

[0247] The number of carbon atoms of the fluorine-containing alkylene group having the keto group is preferably 3 or more. Further, the number of carbon atoms of the fluorine-containing alkylene group having the keto group is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, and particularly preferably 5 or less.

[0248] Specific examples of the fluorine-containing alkylene group having the keto group include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2CF2-, and the like. The fluorine-containing alkylene group having the keto group is preferably a perfluoroalkylene group.

[0249] Water may be added to the keto group in the fluorine-containing alkylene group. Therefore, the monomer (2) may be a hydrate. Examples of the fluorine-containing alkylene group with water added to the keto group include -CF2CF(CF3)C(OH)2-CF2-, -CF2CF(CF3)C(OH)2-CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2CF2-, and the like.

[0250] The monomer represented by the general formula (2) is preferably at least one selected from the group consisting of the monomers represented by the general formulas (2a), (2b), (2c), (2d), (2e), (2f), and (2g). CF2=CF-O-(CF2) n1 -A (2a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) CF2=CF-O-(CF2C(CF3)F) n2 -A (2b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as defined above.) CF2=CF-O-(CFX 1 ) n3 -A (2c) (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, and A is the same as defined above.) CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -A (2d) (In the formula, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and A and X 1 are the same as defined above.) CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-A (2e) (In the formula, n5 represents an integer of 0 to 10, and A and X 1 are the same as defined above.) CF2=CF-O-(CF2) n7 -O-(CF2) n8 -A (2f) (In the formula, n7 represents an integer from 1 to 10, and n8 represents an integer from 1 to 3. A is the same as the above definition.) CF2=CF[OCF2CF(CF3)] n9 O(CF2) n10 O[CF(CF3)CF2O] n11 CF(CF3)-A (2g) (In the formula, n9 represents an integer from 0 to 5, n10 represents an integer from 1 to 8, and n11 represents an integer from 0 to 5. A is the same as the above definition.)

[0251] In general formula (2a), it is preferable that the above n1 is an integer of 5 or less, and more preferably an integer of 2 or less.

[0252] Examples of the monomer represented by general formula (2a) include CF2=CF-O-CF2COOM a , CF2=CF(OCF2CF2COOM a ), CF2=CF(O(CF2)3COOM a ), CF2=CF(OCF2CF2SO3M a ), CF2=CFOCF2SO3M a , CF2=CFOCF2CF2CF2SO3M a (In the formula, M a is the same as the above definition.)

[0253] In general formula (2b), it is preferable that n2 is an integer of 3 or less in terms of the dispersion stability of the resulting composition.

[0254] In general formula (2c), it is preferable that n3 is an integer of 5 or less in terms of water solubility, the above A is preferably -COOM a , and it is preferable that the above M a is H, Na, or NH4.

[0255] In general formula (2d), X 1 is preferably -CF3 in terms of the dispersion stability of the composition, it is preferable that n4 is an integer of 5 or less in terms of water solubility, and A is -COOM ais preferably M a is preferably H, Na or NH4.

[0256] Examples of the monomer represented by the general formula (2d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM a , CF2=CFOCF2CF(CF3)OCF2COOM a , CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM a , CF2=CFOCF2CF(CF3)OCF2SO3M a , CF2=CFOCF2CF(CF3)OCF2CF2SO3M a , CF2=CFOCF2CF(CF3)OCF2CF2CF2SO3M a (wherein M a represents H, NH4 or an alkali metal.)

[0257] In the general formula (2e), n5 is preferably an integer of 5 or less in terms of water solubility, and A is -COOM a is preferably M a is preferably H or NH4.

[0258] Examples of the monomer represented by the general formula (2e) include CF2=CFOCF2CF2CF2COOM a (wherein M a represents H, Na, NH4 or an alkali metal.)

[0259] In the general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, and A is -COOM a or SO3M a is preferably, and -COOM a is more preferable. M a is preferably H, Na, K or NH4.

[0260] Examples of the monomer represented by the general formula (2f) include CF2=CF-O-(CF2)3-O-CF2-COOM a (wherein Ma represents H, NH4, or an alkali metal. Examples include.)

[0261] In general formula (2g), n9 is preferably an integer of 3 or less in terms of water solubility, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, and A is -COOM a or SO3M a is preferably, and -COOM a is more preferable. M a is preferably H, Na, K, or NH4.

[0262] Examples of the monomer represented by general formula (2g) include CF2 = CFO(CF2)2OCF(CF3)COOM a , CF2 = CFOCF2CF2OCF(CF3)CF2OCF(CF3)COOM a , CF2 = CFOCF2CF(CF3)OCF2CF2OCF(CF3)COOM a , CF2 = CF[OCF2CF(CF3)]2O(CF2)2O[CF(CF3)CF2O]CF(CF3)COOM a , CF2 = CF[OCF2CF(CF3)]3O(CF2)2O[CF(CF3)CF2O]3CF(CF3)COOM a (wherein M a represents H, NH4, or an alkali metal. Examples include.)

[0263] The monomer (I) is also preferably the monomer (3) represented by general formula (3). The polymer (I) is also preferably the polymer (3) containing the polymerization unit (3) based on the monomer represented by general formula (3). CX2 = CY(-Rf-A) (3) (wherein X is the same or different and is -H or F, Y is -H, -F, an alkyl group, or a fluorine-containing alkyl group, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. A is the same as described above.)

[0264] In the production method of the present disclosure, the monomer (3) represented by the general formula (3) may be copolymerized with other monomers. The polymer (3) may be a homopolymer of the monomer represented by the general formula (3) or a copolymer with other monomers.

[0265] The fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms does not include a structure in which an oxygen atom is at the terminal, and is an alkylene group containing an ether bond between carbon-carbon bonds.

[0266] In the general formula (3), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In the general formula (3), at least one of X and Y preferably contains a fluorine atom.

[0267] The monomer represented by the general formula (3) is the general formula (3a): CF2=CF-(CF2) n1 -A (3a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) and the monomer represented by the general formula (3b): CF2=CF-(CF2C(CF3)F) n2 -A (3b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as defined above.) At least one selected from the group consisting of monomers is preferred.

[0268] In the general formula (3a) and the general formula (3b), A is -SO3M a or COOM a is preferred, and M a is H, a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium. R 2 represents H or an organic group.

[0269] In the general formula (3a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. A is -COOMa is preferably M a is preferably H or NH4.

[0270] Examples of the monomer represented by the general formula (3a) include CF2 = CFCF2COOM a (where M a is as defined above.)

[0271] In the general formula (3b), n2 is preferably an integer of 3 or less in terms of the dispersion stability of the resulting composition, and A is preferably -COOM a is preferably M a is preferably H or NH4.

[0272] Next, a preferred configuration when m is an integer of 2 or more in the general formula (I) will be described.

[0273] The monomer (I) is also preferably at least one selected from the group consisting of the monomers represented by the general formula (4a) and the general formula (4b). The polymer (I) is also preferably a polymer (4) containing a polymerization unit (4) based on at least one monomer selected from the group consisting of the monomers represented by the general formula (4a) and the general formula (4b). CF2 = CF - CF2 - O - Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4a) (where Z 1 、Z 2 and A are as defined above, Q F1 and Q F2 are the same or different and are a single bond, a fluorine-containing alkylene group which may contain an ether bond between carbon atoms, or a fluorine-containing oxyalkylene group which may contain an ether bond between carbon atoms) CF2 = CF - O - Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4b) (where Z1 , Z 2 , A, Q F1 and Q F2 is the same as the above definition)

[0274] Examples of the monomers represented by general formula (4a) and general formula (4b) include [Chemical formula] and the like.

[0275] As the monomer (I), at least one selected from the group consisting of the monomer (1), the monomer (2), and the monomer (3) is preferable, the monomer (1) is more preferable, and the monomer (1A) is even more preferable. As the polymer (I), at least one selected from the group consisting of the polymer (1), the polymer (2), and the polymer (3) is preferable, and the polymer (1) is more preferable.

[0276] In the present disclosure, the monomer (I) and other monomers may be copolymerized. The polymer (I) may be a homopolymer consisting only of the polymerization unit (I), or may be a copolymer containing the polymerization unit (I) and a polymerization unit based on another monomer copolymerizable with the monomer represented by the general formula (I). From the viewpoint of solubility in an aqueous medium, a homopolymer consisting only of the polymerization unit (I) is preferable. The polymerization unit (I) may be the same or different in each occurrence, and the polymer (I) may contain polymerization units (I) based on two or more different monomers represented by the general formula (I).

[0277] As the other monomer, a monomer represented by the general formula CFR=CR2 (wherein R is independently H, F, or a perfluoroalkyl group having 1 to 4 carbon atoms) is preferable. Further, as the other monomer, a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms is preferable. Examples of the other monomer include CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E isomer), CHF=CHCF3 (Z isomer), and the like. Among them, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2) is preferable in terms of good copolymerizability, and at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride is more preferable. Therefore, the polymerization unit based on the above other monomer is preferably a polymerization unit based on tetrafluoroethylene. The polymerization units based on the above other monomers may be the same or different in each occurrence, and the polymer (I) may contain polymerization units based on two or more different other monomers.

[0278] Examples of the above other monomers also include the general formula (n1-2):

Chemical formula

[0279] Specific examples include CH2=CFCF2-O-Rf 3 , CF2=CF-O-Rf 3 , CF2=CFCF2-O-Rf 3 , CF2=CF-Rf 3 , CH2=CH-Rf 3 , CH2=CH-O-Rf 3 (In the formula, Rf 3 is the same as the above formula (n1-2)) and the like are preferably mentioned.

[0280] Examples of the above other monomers also include the formula (n2-1):

Chemical formula

Chemical formula

[0281] As the above other monomer, the formula (n2-2): CH2=CHO-Rf 5 (n2-2) (wherein Rf 5 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond and having 2 to 100 carbon atoms). Fluorine-containing vinyl ethers represented by the above formula are also included.

[0282] Specific examples of the monomer of the general formula (n2-2) include

Chemical formula

[0283] More specifically,

Chemical formula

[0284] In addition, the general formula (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (wherein Rf 6 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond and having 2 to 100 carbon atoms). Fluorine-containing allyl ethers represented by the above formula, the general formula (n2-4): CH2=CH-Rf 7 (n2-4) (wherein Rf7 Examples also include fluorine-containing vinyl monomers represented by a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond with 2 to 100 carbon atoms).

[0285] Specific examples of the monomers represented by General Formulas (n2-3) and (n2-4) include

Chemical Formula

[0286] Polymer (I) usually has end groups. The end groups are end groups generated during polymerization. Representative end groups are independently selected from hydrogen, iodine, bromine, linear or branched alkyl groups, and linear or branched fluoroalkyl groups, and may optionally additionally contain at least one chain heteroatom. The alkyl group or fluoroalkyl group preferably has 1 to 20 carbon atoms. These end groups generally are generated from the initiator or chain transfer agent used in the formation of Polymer (I), or are generated during the chain transfer reaction.

[0287] In Polymer (I), the content of polymerization unit (I), in order of preference, is 1.0 mol% or more, 3.0 mol% or more, 5.0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, based on all the polymerization units. It is particularly preferred that the content of polymerization unit (I) is substantially 100 mol%, and most preferably Polymer (I) consists only of polymerization unit (I).

[0288] In the polymer (I), the content of the polymerization unit based on the other monomer copolymerizable with the monomer represented by the general formula (I) is preferably, in descending order, 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less with respect to all the polymerization units. The content of the polymerization unit based on the other monomer copolymerizable with the monomer represented by the general formula (I) is particularly preferably substantially 0 mol%, and most preferably the polymer (I) does not contain the polymerization unit based on the other monomer.

[0289] The number average molecular weight of the polymer (I) is preferably 0.1×10 4 or more, more preferably 0.2×10 4 or more, still more preferably 0.3×10 4 or more, even more preferably 0.4×10 4 or more, even more preferably 0.5×10 4 or more, particularly preferably 1.0×10 4 or more, particularly preferably 3.0×10 4 or more, particularly preferably 3.1×10 4 or more, most preferably 75.0×10 4 or less, more preferably 50.0×10 4 or less, still more preferably 40.0×10 4 or less, even more preferably 30.0×10 4 or less, particularly preferably 20.0×10 4 or less. The number average molecular weight and the weight average molecular weight are values calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. When measurement by GPC is not possible, the number average molecular weight of the polymer (I) can be determined from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0290] The lower limit of the weight average molecular weight of the polymer (I) is preferably, in descending order, 0.2×104 Above, 0.4×10 4 Above, 0.6×10 4 Above, 0.8×10 4 Above, 1.0×10 4 Above, 2.0×10 4 Above, 5.0×10 4 Above, 10.0×10 4 Above, 15.0×10 4 Above, 20.0×10 4 Above, 25.0×10 4 Above. Further, as the upper limit of the weight average molecular weight of the polymer (I), in descending order of preference, 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 Below.

[0291] The polymer (I) preferably has an ion exchange rate (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the polymer main chain relative to the ionic group. A precursor group that becomes ionic upon hydrolysis (for example, -SO2F) is not regarded as an ionic group for the purpose of determining the IXR.

[0292] The IXR is preferably 0.5 or more, more preferably 1 or more, still more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. Also, the IXR is more preferably 43 or less, still more preferably 33 or less, and particularly preferably 23 or less.

[0293] As the ion exchange capacity of the polymer (I), in descending order of preference, it is 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.20 meq / g or more, more than 2.20 meq / g, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, 3.50 meq / g or more. The ion exchange capacity is the content of the ionic group (anionic group) of the polymer (I) and is determined by calculation from the composition of the polymer (I).

[0294] In polymer (I), the ionic group (anionic group) is typically distributed along the polymer main chain. The above polymer (I) includes a polymer main chain together with repeating side chains bonded to this main chain, and it is preferable that this side chain has an ionic group.

[0295] It is preferable that polymer (I) contains an ionic group having a pKa of less than 10, more preferably less than 7. The ionic group of polymer (I) is preferably selected from the group consisting of sulfonate, carboxylate, phosphonate, and phosphate.

[0296] The terms "sulfonate, carboxylate, phosphonate, and phosphate" are intended to refer to the respective salts or the respective acids capable of forming salts. When a salt is used, preferably, the salt is an alkali metal salt or an ammonium salt. A preferred ionic group is a sulfonate group.

[0297] It is preferable that polymer (I) has water solubility. Water solubility means the property of being easily dissolved or dispersed in an aqueous medium. A polymer (I) having water solubility can, for example, have its particle size unable to be measured by the dynamic light scattering method (DLS), or exhibit a particle size of 5 nm or less.

[0298] The viscosity of the aqueous solution of polymer (I) is preferably 5.0 mPa·s or more, more preferably 8.0 mPa·s or more, still more preferably 10.0 mPa·s or more, particularly preferably 12.0 mPa·s or more, most preferably 14.0 mPa·s or more, preferably 100.0 mPa·s or less, more preferably 50.0 mPa·s or less, still more preferably 25.0 mPa·s or less, and especially preferably 20.0 mPa·s or less.

[0299] The viscosity of the aqueous solution of polymer (I) can be specified by adjusting the content of polymer (I) in the aqueous solution to 33% by mass with respect to the aqueous solution and measuring the viscosity of the obtained aqueous solution at 20 °C using a tuning fork vibration type viscometer (model number: SV-10) manufactured by A&D Company, Limited.

[0300] The critical micelle concentration (CMC) of polymer (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0301] The critical micelle concentration of polymer (I) can be determined by measuring the surface tension. The surface tension can be measured, for example, with a surface tensiometer CBVP - A3 type manufactured by Kyowa Interface Science Co., Ltd.

[0302] The acid value of polymer (I) is preferably 60 or more, more preferably 90 or more, still more preferably 120 or more, particularly preferably 150 or more, most preferably 180 or more. The upper limit is not particularly limited, but is preferably 300 or less.

[0303] When polymer (I) has an anionic group other than an acid - type functional group, such as - COOM a , - SO3M a , - OSO3M a or C(CF3)2OM a (where M a is a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group), after converting these groups into acid - type groups, it can be measured by acid - base titration.

[0304] The contents of the dimer and trimer of monomer (I) represented by general formula (I) are preferably 1.0% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, particularly preferably 0.001% by mass or less, and most preferably 0.0001% by mass or less with respect to polymer (I).

[0305] The above-mentioned timer and trimmer can be removed by ultrafiltration, microfiltration, dialysis membrane treatment, etc.

[0306] Compound (II) is represented by the general formula (II). General formula (II): T X -X A -R FA1 -R FA2 -X A -T X ’ (II) (In the formula, R FA1 is -Rf 1 p -R F -O q - and R FA2 is -Rf 2 p -R FX -O q - and R F is a divalent fluoropolyether group, R FX is a divalent fluoropolyether group containing an anionic group, Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms, p is each independently 0 or 1, q is each independently 0 or 1, X A is each independently a single bond or a group with a valence of 2 to 10, T X and T X ’ are each independently selected from the group consisting of (i) a C1-C 24 (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and does not have the above-mentioned anionic group, and (ii) a C1-C 24 (hydro)(fluoro)carbon group containing at least one of the above-mentioned anionic groups.

[0307] In formula (II), R FA1 is -Rf 1 p -R F -O q -.

[0308] In formula (II), R FA2 is -Rf 2 p -R FX -O q -.

[0309] In formula (II), Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms.

[0310] The "C 1-6 alkylene group" in the above-mentioned C 1-6 alkylene group which may be substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-3 alkylene group, more preferably a linear C 1-3 alkylene group.

[0311] Rf 1 and Rf 2 are preferably a C 1-6 alkylene group substituted by one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, still more preferably a C 1-3 perfluoroalkylene group.

[0312] The above-mentioned C 1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0313] In the above formula, p is, independently of each other, 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0314] In the above formula, q is, independently of each other, 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0315] In formula (II), R F is a divalent fluoropolyether group.

[0316] R F is preferably a group of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [wherein: R Fa is, independently of each other, a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are, independently of each other, integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.] and is a group represented by.

[0317] R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.

[0318] a, b, c, d, e, and f are each independently preferably an integer from 0 to 100, more preferably an integer from 0 to 50.

[0319] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and may be, for example, 25 or more or 30 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0320] These repeating units may be linear, branched, or may contain a ring structure. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0321] The above ring structure may be a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring described below.

Chemical formula

[0322] The above ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0323] The repeating unit having a ring structure may preferably be the following unit.

Chemical formula

[0324] In one aspect, the above repeating unit is linear.

[0325] In one aspect, the above repeating unit is branched.

[0326] In one aspect, R F is a group represented by any of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1, preferably 0.], -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more, the order of existence of each repeating unit enclosed in parentheses with c, d, e, or f is arbitrary in the formula.], -(R6 -R 7 ) g - (f3) [wherein, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, and g is an integer from 2 to 100.], -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [wherein, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g’ is an integer from 2 to 100, R r is

Chemical Formula

[0327] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). In one embodiment, e is 0. In another embodiment, e is 1. (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2).

[0328] In the above formula (f2), e and f are each independently, preferably an integer of 5 to 200, more preferably 10 to 200. Also, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f a group represented by -. In another embodiment, the formula (f2) may be a group represented by -(OC2F4) e -(OCF2) f -.

[0329] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7 is preferably a group selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably OC3F6 or OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 is not particularly limited, and examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12may be either linear or branched, preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g -.

[0330] In the above formula (f4), R 6 , R 7 and g have the same meanings as described for the above formula (f3) and have similar embodiments. R 6’ , R 7’ and g' each have the same meanings as R 6 , R 7 and g described in the above formula (f3) and have similar embodiments. R r is preferably [Chemical formula] [In the formula, * indicates the bonding position.] and more preferably [Chemical formula] [In the formula, * indicates the bonding position.] .

[0331] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0332] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0333] In one embodiment, R F is a group represented by the above formula (f1).

[0334] In one embodiment, R Fis a group represented by the above formula (f2).

[0335] In one embodiment, R F is a group represented by the above formula (f3) or (f4).

[0336] In one embodiment, R F is a group represented by the above formula (f3).

[0337] In one embodiment, R F is a group represented by the above formula (f4).

[0338] In one embodiment, R F is a group represented by the above formula (f5).

[0339] In one embodiment, R F is a group represented by the above formula (f6).

[0340] R F In R, the ratio of e to f (hereinafter referred to as "e / f ratio") is preferably from 0.1 to 10, more preferably from 0.2 to 5, still more preferably from 0.2 to 2, even more preferably from 0.2 to 1.5, and particularly preferably from 0.2 to 0.85. By setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The greater the e / f ratio, the more the stability of the compound can be improved.

[0341] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, more preferably from 1.0 to 2.0.

[0342] In formula (II), R FX is a divalent fluoropolyether group containing an anionic group. In addition to anionic groups such as sulfate groups and carboxylate groups, the above anionic groups include functional groups that give anionic groups such as acid groups like -COOH and acid salts like -COONH4. Preferred anionic groups include sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, or -C(CF3)2OM a (wherein M a is -H, a metal atom, -NR 2 4, optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, and R 2 is H or an organic group.)

[0343] R FX The above fluoropolyether group in R may be a group in which one or more hydrogen atoms of the polyether group are substituted with fluorine atoms, and is preferably a perfluoropolyether group.

[0344] R FX As repeating units, (a1)-CF2CF(G x )O- (b1)-CF(G x )O- (c1)-CF2(CF2) x1 CF(G x )(CF2) x2 O-(X1 and X2 are zero or integers from 1 to 2, provided that X1 + X2 is at least 1) [wherein G x is a C1-C5 perfluoro(oxy)alkylene group containing at least one anionic group as detailed above] and is preferably a divalent fluoropolyether group having units selected from the group consisting of

[0345] Note that the order of the repeating units constituting R F and R FX is arbitrary.

[0346] In the above compound (II), R FA1 and R FA2 The number average molecular weight of the part is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, R FA1 and R FA2 The number average molecular weight of is 19 The value measured by 19F-NMR.

[0347] In formula (II), X A is understood to be a linker that connects the fluoropolyether part (R FA1 and R FA2 ) and the part containing an anionic group (T X and T X ’). Therefore, the X A may be a single bond or any group as long as the compound represented by formula (II) can exist stably.

[0348] X A is each independently a single bond or a divalent to decavalent group.

[0349] X A is each independently preferably a single bond or a divalent to decavalent organic group.

[0350] In one embodiment, X A does not contain a siloxane bond (-Si-O-Si-).

[0351] The divalent to decavalent group in the above X A is preferably a divalent to octavalent group. In one embodiment, such a divalent to decavalent group is preferably a divalent to tetravalent group, more preferably a divalent group. In another embodiment, such a divalent to decavalent group is preferably a trivalent to octavalent group, more preferably a trivalent to hexavalent group.

[0352] In one embodiment, X A is a single bond or a divalent group.

[0353] The divalent group is preferably an oxygen atom, a sulfur atom, NH, CO, or a divalent organic group, more preferably an oxygen atom or a divalent organic group, still more preferably a divalent organic group.

[0354] In one embodiment, X A is a group having a valence of 3 to 6, preferably a trivalent to hexavalent organic group.

[0355] In one embodiment, X A is a trivalent group, preferably a trivalent organic group.

[0356] In one embodiment, X A is a single bond.

[0357] In another embodiment, X A is a divalent organic group.

[0358] In one embodiment, X A is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [wherein: R 51 represents a single bond, -(CH2) s5 -, or an o-, m-, or p-phenylene group, preferably -(CH2) s5 -, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and still more preferably 1 or 2, X 51 represents -(X 52 ) l5 -, X 52 each independently represents -O-, -S-, o-, m-, or p-phenylene group, -C(O)O-, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -, -O-CONR 54 -, -NR54 - and -(CH2) n5 represents a group selected from the group consisting of, R 53 each independently represents a phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group, preferably a phenyl group or C 1-6 alkyl group, more preferably a methyl group, R 54 each independently represents a hydrogen atom, a phenyl group or C 1-6 alkyl group (preferably a methyl group), m5, in each occurrence, is each independently an integer from 1 to 100, preferably an integer from 1 to 20, n5, in each occurrence, is each independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, l5 is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the order of existence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary, the right side is bonded to T X and T X ’.] Examples of the divalent organic group represented by. Here, X A (typically the hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, C 1-3 alkyl group and C 1-3 fluoroalkyl group. In a preferred embodiment, X A is not substituted with these groups.

[0359] In a preferred embodiment, the above X A each independently is -(R 51 ) p5 -(X 51 ) q5 -R 52 -. R52 represents a single bond, -(CH2) t5 - or an o-, m- or p-phenylene group, preferably -(CH2) t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Here, R 52 (typically a hydrogen atom of R 52 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. In a preferred embodiment, R 52 is not substituted with these groups.

[0360] Preferably, the above X A are each independently a single bond, a C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 5 - [wherein, R 51 and R 52 are as defined above, X 53 is -O-, -S-, -C(O)O-, -CONR 54 (-), -O-CONR 54 (-), -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -Si(R 53)2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-, -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54 -(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -(CH2) u5 -N(R 54 )- or -CONR 54 -(o-, m- or p-phenylene)-Si(R 53 )2- (In the formula, R 53 , R 54 and m5 are as defined above; u5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. X 54 teeth, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-, -CONR 54 -(CH2) u5 -N(R 54 )- or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (In the formula, each symbol has the same meaning as above.) represents.] It could be.

[0361] More preferably, the above X A is, independently of each other, a single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -、 -(CH2) s5 -X 53 -(CH2) t5 - -X 54 -、or -X 54 -(CH2) t5 - [wherein X 53 , X 54 , s5 and t5 have the same meanings as defined above.] is.

[0362] More preferably, the above X A is, independently of each other, a single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -(CH2) t5 -、or -X 54 -(CH2) t5 - [wherein each symbol has the same meaning as defined above.] can be.

[0363] In a preferred embodiment, the above X A is, independently of each other, a single bond C 1-20 an alkylene group, -(CH2) s5 -X 53 -、or -(CH2) s5 -X 53 -(CH2) t5 - [wherein X 53 is -O-, -CONR 54 -, or -O-CONR 54- and R 54 each independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20.] It can be.

[0364] In a preferred embodiment, the above X A each independently is -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [wherein, R 54 each independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20.] It can be.

[0365] In one embodiment, the above X A each independently is a single bond, a C 1-20 alkylene group, -(CH2) s5 -O-(CH2) t5 -, -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, or -(CH2) s5 -O-(CH2) t5 -Si(R 53)2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [wherein, R 53 , m5, s5, t5 and u5 have the same meanings as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.] is as follows.

[0366] In the above formula, -(C v H 2v )- may be linear or branched, and examples thereof include -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0367] Each of the above X A may be independently substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). In one embodiment, X A is unsubstituted.

[0368] In one embodiment, each of X A may be independently other than an -O-C 1-6 alkylene group.

[0369] In another embodiment, examples of X A include the following groups: [Chemical formula] [Chemical formula] [wherein, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group, D is -CH2O(CH2)2-, -CH2O(CH2)3-、 -CF2O(CH2)3-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -CONH-(CH2)3-、 -CON(CH3)-(CH2)3-、 -CON(Ph)-(CH2)3- (wherein Ph represents phenyl), and

Chemical formula

[0370] Specific examples of the above X A are, for example: A single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -CH2OCF2CHFOCF2-、 -CH2OCF2CHFOCF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-、 -CH2OCH2CF2CF2OCF2-、 -CH2OCH2CF2CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -(CH2)5-、 -(CH2)6-、 -CO-、 -CONH-、 -CONH-CH2-、 -CONH-(CH2)2-、 -CONH-(CH2)3-、 -CONH-(CH2)4-、 -CONH-(CH2)5-、 -CONH-(CH2)6-、 -CON(CH3)-CH2-、 -CON(CH3)-(CH2)2-、 -CON(CH3)-(CH2)3-、 -CON(CH3)-(CH2)4-、 -CON(CH3)-(CH2)5-、 -CON(CH3)-(CH2)6-、 -CON(Ph)-CH2-(where Ph means phenyl), -CON(Ph)-(CH2)2-(where Ph means phenyl), -CON(Ph)-(CH2)3-(where Ph means phenyl), -CON(Ph)-(CH2)4-(where Ph means phenyl), -CON(Ph)-(CH2)5-(where Ph means phenyl), -CON(Ph)-(CH2)6-(where Ph means phenyl), -CONH-(CH2)2NH(CH2)3-、 -CONH-(CH2)6NH(CH2)3-、 -CH2O-CONH-(CH2)3-、 -CH2O-CONH-(CH2)6-、 -S-(CH2)3-、 -(CH2)2S(CH2)3-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -C(O)O-(CH2)3-、 -C(O)O-(CH2)6-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、 -OCH2-、 -O(CH2)3-、 -OCFHCF2-、

Chem.

[0371] In yet another aspect, X A is, independently of each other, a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 -. In the formula, x1, y1 and z1 are, independently of each other, integers from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

[0372] In the above formula, R 16 is, independently of each other, an oxygen atom, a phenylene, a carbazolylene, -NR 18 -(in the formula, R 18 represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, R 18 is an oxygen atom or a divalent polar group.

[0373] The above "divalent polar group" is not particularly limited, but -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 -(in these formulas, R 19 represents a hydrogen atom or a lower alkyl group) can be mentioned. The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, and these may be substituted by one or more fluorine atoms.

[0374] In the above formula, R 17 is, independently of each other, a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and still more preferably a trifluoromethyl group.

[0375] Furthermore, the above X A has, on the left side of each formula, R FA1 or R FA2 bonded thereto, and on the right side, T X and T X ' bonded thereto.

[0376] In yet another aspect, examples of X A include the following groups: [Chemical formula] [wherein R 41 is, independently of each other, a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group, in each X A group, some of the Ts, optionally, are the following groups bonded to R FA1 or R FA2 in the main molecular chain: -CH2O(CH2)2-, -CH2O(CH2)3-, -CF2O(CH2)3-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -CONH-(CH2)3-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph means phenyl), or [Chemical formula] [wherein R 42 is, independently of each other, a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.] is such that some of the other Ts are bonded to R Si in the main molecular chain, and, when present, the remaining Ts are, independently of each other, a methyl group, a phenyl group, a C1-6 It is an alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.

[0377] The radical scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation. Examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic esters, organoacrylates, hindered amines, hindered phenols, or triazines.

[0378] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. Examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxysinnamates, oxamides, oxanilides, benzoxazinones, benzoxazoles.

[0379] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include

Chemical formula

[0380] In this embodiment, X A can each independently be a group having a valence of 3 to 10.

[0381] In yet another embodiment, examples of X A include the following groups:

Chemical formula

[0382] In one embodiment, R 25 is a single bond, C 1-20 alkylene group, C 3-20 cycloalkylene group, C 5-20 arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -. Above, R 57 and R 59 are each independently a single bond, C 1-20 alkylene group, C 3-20 cycloalkylene group, or C 5-20 arylene group. Above, X 58 is -O-, -S-, -CO-, -O-CO- or -COO-.

[0383] In one embodiment, R 26 and R 27 are each independently a hydrocarbon, or a group having at least one atom selected from N, O and S in the end or main chain of the hydrocarbon, preferably C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-, etc. are mentioned. Here, R 36 are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R 37 is N, O or S, preferably N or O. R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 - or -R 45 -R 46 -. Here, R 45 are each independently an alkyl group having 1 to 6 carbon atoms. R 46is N, O or S, preferably O.

[0384] In this embodiment, X A can each independently be a group having a valence of 3 to 10.

[0385] In yet another embodiment, X A is as follows: [Chemical formula] [wherein X a is a single bond or a divalent organic group.] is a group represented by

[0386] The above X a is a single bond or a divalent linking group directly bonded to the isocyanurate ring. X a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.

[0387] X a is as follows: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (wherein X 121 to X 124 are each independently H, F, OH, or -OSi(OR 121 )3 (wherein the three Rs 121 are each independently an alkyl group having 1 to 4 carbon atoms.) and the above X a1is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is bonded to CX 121 X 122 .), x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.). The group represented by

[0388] The above X a1 is preferably -O- or -C(=O)O-.

[0389] The above X a is the following formula: -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - (where m11 is an integer from 1 to 3, m12 is an integer from 1 to 3, and m13 is an integer from 1 to 3.). The group represented by -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - (where m14 is an integer from 1 to 3, m15 is an integer from 1 to 3, and m16 is an integer from 1 to 3.). The group represented by -(CF2) m17 -(CH2) m18 - (where m17 is an integer from 1 to 3, m18 is an integer from 1 to 3.). The group represented by -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - (where m19 is an integer from 1 to 3, m20 is an integer from 1 to 3, and m21 is an integer from 1 to 3.). The group represented by, or -(CH2) m22 - (wherein m22 is an integer from 1 to 3.) The group represented by is particularly preferred.

[0390] The above X a is not particularly limited as, specifically, -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, -(CF2) n5 -(n5 is an integer from 0 to 4.), -(CF2) n5 -(CH2) m5 -(n5 and m5 are each independently an integer from 0 to 4.), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- and the like can be mentioned.

[0391] In this embodiment, X A can each independently be a divalent or trivalent group.

[0392] In one embodiment, the compound (II) represented by formula (II) does not contain a siloxane bond (-Si-O-Si-).

[0393] The compound (II) is not particularly limited, but can have a number average molecular weight of 5×10 2 ~1×10 5 . Among such a range, it is preferable from the viewpoint of polymerization stability to have a number average molecular weight of preferably 2,000 or more, more preferably 2,500 or more as the lower limit, and preferably 32,000 or less, more preferably 12,000 or less as the upper limit. The number average molecular weight of the compound (II) is 19 a value measured by 19F-NMR.

[0394] In one aspect, the number average molecular weight of compound (II) can preferably be 500 or more, more preferably 1,000 or more, still more preferably 2,000 or more, even more preferably 3,000 or more, and can preferably be 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, even more preferably 10,000 or less, and particularly preferably 6,000 or less.

[0395] In another aspect, the number average molecular weight of compound (II) can preferably be 4,000 or more, more preferably 5,000 or more, and more preferably 6,000 or more, and can preferably be 30,000 or less, more preferably 10,000 or less.

[0396] Examples of compound (II) include the compounds described in International Publication No. 2019 / 048394.

[0397] The content of the above polymer compound in the TFE-based polymer composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, based on the above TFE-based polymer.

[0398] The content of the above polymer compound in the TFE-based polymer composition is determined by solid-state NMR measurement. In addition, the measurement methods of respective polymers are described in WO 2014 / 099453, WO 2010 / 075497, WO 2010 / 075496, WO 2011 / 008381, WO 2009 / 055521, WO 1987 / 007619, JP-A-61-293476, WO 2010 / 075494, WO 2010 / 075359, WO 2012 / 082454, WO 2006 / 119224, WO 2013 / 085864, WO 2012 / 082707, WO 2012 / 082703, WO 2012 / 082451, WO 2006 / 135825, WO 2004 / 067588, WO 2009 / 068528, JP-A-2004-075978, JP-A-2001-226436, WO 1992 / 017635, WO 2014 / 069165, JP-A-11-181009, etc. As the measurement method of the content of the above polymer compound, the measurement methods of respective polymers described therein can be used.

[0399] A TFE-based polymer composition containing a polymer compound having an ionic group can be obtained, for example, by polymerization using the above polymer compound.

[0400] The TFE-based polymer composition of the present disclosure preferably contains substantially no moisture. Thereby, generation of gas and deterioration of electrochemical device characteristics can be suppressed. In addition, since electrode active materials and solid electrolytes to be combined can be widely selected, it is advantageous in terms of production processes. Containing substantially no moisture means that the moisture content with respect to the above TFE-based polymer composition is 0.010% by mass or less. The above moisture content is preferably 0.005% by mass or less, more preferably 0.003% by mass or less, still more preferably 0.002% by mass or less, and still more preferably 0.001% by mass or less. The above moisture content is measured by the following method. Measure the mass of the TFE-based polymer composition before and after heating at 150°C for 2 hours, and calculate according to the following formula. Take three samples, calculate each one, then find the average and adopt the average value. Moisture content (mass%) = [(mass of the TFE-based polymer composition before heating (g)) - (mass of the TFE-based polymer composition after heating (g))] / (mass of the TFE-based polymer composition before heating (g)) × 100

[0401] The TFE-based polymer composition of the present disclosure is non-melt processable.

[0402] The TFE-based polymer composition of the present disclosure has an apparent density of less than 0.50 g / ml, but in terms of reducing resistance, improving adhesion to the substrate, and improving cycle characteristics, and in terms of obtaining a composite sheet excellent in strength and flexibility, it is preferably 0.45 g / ml or less, more preferably 0.43 g / ml or less, still more preferably 0.40 g / ml or less, even more preferably less than 0.40 g / ml, and also preferably 0.10 g / ml or more, more preferably 0.15 g / ml or more, still more preferably 0.20 g / ml or more, even more preferably 0.25 g / ml or more, still more preferably 0.30 g / ml or more, and particularly preferably 0.35 g / ml or more. The above apparent density is measured in accordance with JIS K 6892.

[0403] The TFE-based polymer composition of the present disclosure may have a 1.0% mass loss temperature of 492°C or less. A TFE-based polymer composition having a 1.0% mass loss temperature of 492°C or less is obtained by using a hydrocarbon-based surfactant. The above 1.0% mass loss temperature is the value measured by the following method. Precisely weigh approximately 10 mg of a TFE-based polymer composition without a heating history at a temperature of 300 °C or higher, store it in a dedicated aluminum pan, and measure it using a TG·DTA (differential thermal and thermogravimetric simultaneous measurement device). The 1.0% mass loss temperature is defined as the temperature corresponding to the point where the weight has decreased by 1.0 mass% when the aluminum pan is heated from 25 °C to 600 °C in an air atmosphere at a rate of 10 °C / min.

[0404] The TFE-based polymer composition of the present disclosure may have a thermal stability index (TII) of 20 or more. A TFE-based polymer composition with a TII of 20 or more is obtained by using a hydrocarbon-based surfactant. The TII is preferably 25 or more, more preferably 30 or more, still more preferably 35 or more, and particularly preferably 40 or more. The TII is also preferably 50 or less. The above TII is measured in accordance with ASTM D 4895-89.

[0405] The TFE-based polymer composition of the present disclosure preferably has an endothermic peak temperature of 333 °C or higher, more preferably 335 °C or higher, still more preferably 337 °C or higher, even more preferably 340 °C or higher, and also preferably 350 °C or lower, more preferably 346 °C or lower, in that it can form a sizing agent sheet with even better strength. The above endothermic peak temperature is the temperature corresponding to the minimum point in the melting heat curve obtained by performing differential scanning calorimetry [DSC] on a TFE-based polymer composition without a heating history at a temperature of 300 °C or higher at a heating rate of 10 °C / min. When there are two or more minimum points in one melting peak, each is taken as the endothermic peak temperature.

[0406] The TFE-based polymer composition of the present disclosure preferably has a melting point of 315 °C or higher, more preferably 320 °C or higher, still more preferably 323 °C or higher, even more preferably 325 °C or higher, and also preferably 335 °C or lower, more preferably 330 °C or lower, in that it can form a sizing agent sheet with even better strength. The melting point is the temperature corresponding to the minimum point in the heat of fusion curve obtained by performing differential scanning calorimetry [DSC] on a TFE-based polymer composition having a heating history at a temperature of 300 °C or higher at a heating rate of 10 °C / min.

[0407] The TFE-based polymer composition of the present disclosure preferably has a standard specific gravity (SSG) of 2.280 or less, more preferably 2.250 or less, still more preferably 2.220 or less, still more preferably 2.200 or less, still more preferably 2.190 or less, particularly preferably 2.180 or less, and especially preferably 2.170 or less, in that it can form a composite sheet with even better strength. The above SSG is preferably 2.130 or more. The above SSG is measured by the water displacement method in accordance with ASTM D 792 using a sample molded in accordance with ASTM D 4895 89.

[0408] The TFE-based polymer composition of the present disclosure may have an average secondary particle diameter of 350 μm or more, preferably 400 μm or more, more preferably 450 μm or more, and preferably 1000 μm or less, more preferably 900 μm or less, still more preferably 800 μm or less, still more preferably 700 μm or less, and particularly preferably 600 μm or less. The above average secondary particle diameter is measured in accordance with JIS K 6891.

[0409] The form of the TFE-based polymer composition of the present disclosure is not limited, but it is preferably a powder in that it can be mixed with an electrode active material or a solid electrolyte without using a large amount of a dispersion medium. Note that the TFE-based polymer composition may be in a form other than a powder, for example, it may be a dispersion.

[0410] The TFE-based polymer composition of the present disclosure can be preferably produced by a production method including, for example, step (A) of preparing an aqueous dispersion of a TFE-based polymer, step (B) of coagulating the aqueous dispersion to obtain a wet powder, and step (C) of drying the wet powder.

[0411] Step (A) is preferably step (A1) of obtaining an aqueous dispersion of a TFE-based polymer by emulsion polymerization of TFE and a monomer having a polar group in an aqueous medium in the presence of an anionic fluorine-containing surfactant.

[0412] The emulsion polymerization in step (A1) can be carried out by a known method. For example, by carrying out emulsion polymerization of the monomers necessary to constitute the TFE-based polymer in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator, an aqueous dispersion containing particles (primary particles) of the TFE-based polymer is obtained. In the above emulsion polymerization, a chain transfer agent, a buffer, a pH adjuster, a co-stabilizer, a dispersion stabilizer, a radical scavenger, etc. may be used as necessary.

[0413] The above emulsion polymerization can be carried out, for example, in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator. For the above emulsion polymerization, an aqueous medium, the above anionic fluorine-containing surfactant, a monomer, and other additives as necessary are charged into a polymerization reactor, the contents of the reactor are stirred, and the reactor is maintained at a predetermined polymerization temperature. Then, a predetermined amount of a polymerization initiator is added to start the polymerization reaction. After the start of the polymerization reaction, monomers, polymerization initiators, chain transfer agents, and the above surfactants, etc. may be additionally added according to the purpose.

[0414] The above polymerization initiator is not particularly limited as long as it can generate radicals in the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Further, polymerization can also be started as a redox in combination with a reducing agent or the like. The concentration of the above polymerization initiator is appropriately determined according to the type of monomer, the molecular weight of the target TFE-based polymer, and the reaction rate.

[0415] As the polymerization initiator described above, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0416] The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, such as dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, etc. Also, di(ω-hydroxy-dodecafluorooctanoyl) peroxide, di(ω-hydroxy-tetradecafluorooctanoyl) peroxide, di(ω-hydroxy-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di(ω-chloro-hexafluorobutyryl) peroxide, di(ω-chloro-decafluorohexanoyl) peroxide, di(ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydroxy-dodecafluorooctanoyl-ω-hydroxy-hexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydroxy-dodecafluorooctanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl) peroxide, di(trichlorooctafluorohexanoyl) peroxide, di(tetrachloroundecafluorooctanoyl) peroxide, di(pentachlorotetradecafluorodecanoyl) peroxide, di(undecachlorodotriacontapentafluorodocosanoyl) peroxide, di[perfluoro(or fluorochloro)acyl] peroxides, etc. are mentioned as typical ones.

[0417] The water-soluble radical polymerization initiator may be a known water-soluble peroxide. For example, ammonium salts, potassium salts, sodium salts, such as persulfuric acid, perboric acid, perchloric acid, phosphoric acid, percarbonic acid, etc., t-butyl permaleate, t-butyl hydroperoxide, succinic peroxide, etc. may be mentioned. Among them, ammonium persulfate and succinic peroxide are preferred. Reducing agents such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.

[0418] The addition amount of the water-soluble radical polymerization initiator is not particularly limited, but it may be added all at once, sequentially, or continuously at the initial stage of polymerization in an amount such that the polymerization rate does not decrease significantly (for example, several ppm with respect to the water concentration) or more. The upper limit is in a range where the reaction temperature may be increased while removing the polymerization reaction heat from the equipment surface, and a more preferable upper limit is in a range where the polymerization reaction heat can be removed from the equipment surface. In terms of easily obtaining the above-described various physical properties, the addition amount of the polymerization initiator is preferably an amount corresponding to 0.1 ppm or more with respect to the aqueous medium, more preferably an amount corresponding to 1.0 ppm or more, and preferably an amount corresponding to 100 ppm or less, more preferably an amount corresponding to 10 ppm or less.

[0419] For example, when polymerization is carried out at a low temperature of 30°C or lower, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, ammonium cerium nitrate, bromates, etc. Examples of the reducing agent include sulfites, bisulfites, bromates, diimines, oxalic acid, etc. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the sulfite include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the combination of the redox initiator. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate.

[0420] As the redox initiator, it is preferable that the oxidizing agent is permanganic acid or its salt, persulfate, manganese triacetate, cerium(IV) salt, or bromic acid or its salt, and the reducing agent is dicarboxylic acid or its salt, or diimine. More preferably, the oxidizing agent is permanganic acid or its salt, persulfate, or bromic acid or its salt, and the reducing agent is dicarboxylic acid or its salt.

[0421] Examples of the redox initiator include combinations such as potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, manganese triacetate / oxalic acid, manganese triacetate / ammonium oxalate, ammonium cerium nitrate / oxalic acid, ammonium cerium nitrate / ammonium oxalate, and the like. When using a redox initiator, either the oxidizing agent or the reducing agent may be charged into the polymerization tank in advance, and then the other may be added continuously or intermittently to initiate polymerization. For example, when using potassium permanganate / oxalic acid, it is preferable to charge oxalic acid into the polymerization tank and continuously add potassium permanganate thereto. In the redox initiator of this specification, when "potassium permanganate / oxalic acid" is described, it means the combination of potassium permanganate and oxalic acid. The same applies to other compounds.

[0422] The redox initiator is particularly preferably a combination of an oxidizing agent that is a salt and a reducing agent that is a salt. For example, the oxidizing agent that is a salt is more preferably at least one selected from the group consisting of persulfate, permanganate, cerium(IV) salt, and bromate, still more preferably permanganate, and particularly preferably potassium permanganate. Also, the reducing agent that is a salt is more preferably at least one selected from the group consisting of oxalate, malonate, succinate, glutarate, and bromate, still more preferably oxalate, and particularly preferably ammonium oxalate.

[0423] Specific examples of the redox initiator preferably include at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, manganese triacetate / ammonium oxalate, and ammonium cerium nitrate / ammonium oxalate. More preferably, it is at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, and ammonium cerium nitrate / ammonium oxalate. Even more preferably, it is potassium permanganate / oxalic acid.

[0424] When using a redox initiator, the oxidizing agent and the reducing agent may be added all at once at the initial stage of polymerization, or the reducing agent may be added all at once at the initial stage of polymerization and the oxidizing agent may be added continuously, or the oxidizing agent may be added all at once at the initial stage of polymerization and the reducing agent may be added continuously, or both the oxidizing agent and the reducing agent may be added continuously.

[0425] When adding one of the redox polymerization initiators first and continuously adding the other one at the initial stage of polymerization, it is preferable to gradually reduce the addition rate in terms of obtaining a TFE-based polymer with a low SSG, and it is more preferable to stop the polymerization during the process. The preferable time to stop the addition is before 20 to 40% by mass of all the TFE consumed in the polymerization reaction is consumed.

[0426] When using a redox initiator as the polymerization initiator, for the aqueous medium, the addition amount of the oxidizing agent is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, still more preferably 0.5 ppm or more, even more preferably 1 ppm or more, particularly preferably 5 ppm or more, and extremely preferably 10 ppm or more. Also, it is preferably 10000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and even more preferably 50 ppm or less. The addition amount of the reducing agent is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, still more preferably 3 ppm or more, even more preferably 5 ppm or more, particularly preferably 10 ppm or more. Also, it is preferably 10000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and even more preferably 50 ppm or less. Also, when using a redox initiator in the above emulsion polymerization, the polymerization temperature is preferably 100 °C or lower, more preferably 95 °C or lower, and still more preferably 90 °C or lower. Also, it is preferably 10 °C or higher, more preferably 20 °C or higher, and still more preferably 30 °C or higher.

[0427] As the above polymerization initiator, a water-soluble radical polymerization initiator and a redox initiator are preferable in terms of easily obtaining the above-described physical properties.

[0428] The above aqueous medium is a reaction medium for carrying out the polymerization and means a liquid containing water. The above aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as alcohol, ether, or ketone, and / or a fluorine-containing organic solvent having a boiling point of 40 °C or lower.

[0429] In the above emulsion polymerization, if necessary, a nucleating agent, a chain transfer agent, a buffer, a pH adjuster, a stabilization aid, a dispersion stabilizer, a radical scavenger, a decomposer of the polymerization initiator, a dicarboxylic acid, etc. may be used.

[0430] For the purpose of adjusting the particle size, it is preferable to carry out the above emulsion polymerization by adding a nucleating agent. It is preferable to add the nucleating agent before the start of the polymerization reaction. As the above nucleating agent, known ones can be used. For example, it is preferably at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents, and more preferably a nonionic surfactant.

[0431] Examples of the above fluoropolyether include perfluoropolyether (PFPE) acid or its salt. The above perfluoropolyether (PFPE) acid or its salt may have an arbitrary chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Also, two or more types of fluorocarbon groups may be present in the molecule. A typical structure has a repeating unit represented by the following formula: (-CFCF3-CF2-O-) n (-CF2-CF2-CF2-O-) n (-CF2-CF2-O-) n -(-CF2-O-) m (-CF2-CFCF3-O-) n -(-CF2-O-) m

[0432] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed in this document, the PFPE acid or its salt may have a carboxylic acid group or its salt at one or both ends. The PFPE acid or its salt may also have a sulfonic acid, phosphonic acid group or their salts at one or both ends. Further, the PFPE acid or its salt may have different groups at each end. For monofunctional PFPE, the other end of the molecule is usually perfluorinated, but may contain a hydrogen or chlorine atom. The PFPE acid or its salt has at least two ether oxygens, preferably at least four ether oxygens, even more preferably at least six ether oxygens. Preferably, at least one of the fluorocarbon groups separating the ether oxygens, more preferably at least two of such fluorocarbon groups, has two or three carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have two or three carbon atoms. Also preferably, the PFPE acid or its salt has a total of at least 15 carbon atoms. For example, the preferred minimum value of n or n + m in the repeating unit structure above is at least 5. Two or more of the above PFPE acids or their salts having an acid group at one or both ends can be used in the production method of the present disclosure. The PFPE acid or its salt preferably has a number average molecular weight of less than 6000 g / mol.

[0433] In terms of being able to further increase the molecular weight of the TFE-based polymer and improve the strength of the composite sheet, it is preferable to carry out the emulsion polymerization by adding a radical scavenger or a decomposer of the polymerization initiator. The radical scavenger or the decomposer of the polymerization initiator is preferably added after the start of the polymerization reaction, preferably before 10% by mass or more, preferably 20% by mass or more of the total TFE consumed in the polymerization reaction is polymerized, and also preferably before 50% by mass or less, preferably 40% by mass or less is polymerized. When depressurization and subsequent repressurization described later are carried out, it is preferably added thereafter.

[0434] As the radical scavenger, a compound that does not have a restarting ability after addition to or chain transfer with free radicals in the polymerization system is used. Specifically, a compound that easily undergoes a chain transfer reaction with primary radicals or growing radicals and then generates stable radicals that do not react with monomers, or a compound that has a function of easily undergoing an addition reaction with primary radicals or growing radicals to generate stable radicals is used. What is generally called a chain transfer agent is characterized by its activity in terms of a chain transfer constant and a restart efficiency. Among chain transfer agents, those with a restart efficiency of almost 0% are called radical scavengers. The radical scavenger can also be, for example, a compound in which the chain transfer constant with TFE at the polymerization temperature is larger than the polymerization rate constant and the restart efficiency is substantially 0%. "The restart efficiency is substantially 0%" means that the generated radicals are converted into stable radicals by the radical scavenger. Preferably, it is a compound in which the chain transfer constant (Cs) with TFE at the polymerization temperature (= chain transfer rate constant (kc) / polymerization rate constant (kp)) is greater than 0.1. For the above compound, it is more preferable that the chain transfer constant (Cs) is 0.5 or more, still more preferable that it is 1.0 or more, even more preferable that it is 5.0 or more, and particularly preferable that it is 10 or more.

[0435] As the radical scavenger, for example, at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N - diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl2) is preferable. Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m - or p - salicylic acid, gallic acid, naphthol, etc. Examples of the unsubstituted phenol include о -, m - or p - nitrophenol, о -, m - or p - aminophenol, p - nitrosophenol, etc. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, naphthoresorcinol, etc. Examples of the aromatic amines include o-, m- or p-phenylenediamine, benzidine and the like. Examples of the quinone compounds include o-, m- or p-benzoquinone, 1,4-naphthoquinone, alizarin and the like. Examples of the thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN) and the like. Among the radical scavengers, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

[0436] From the viewpoint of moderately reducing the standard specific gravity, the addition amount of the radical scavenger is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration. A more preferable lower limit is 10% (molar basis), and even more preferably 15% (molar basis). A more preferable upper limit is 400% (molar basis), and even more preferably 300% (molar basis).

[0437] The decomposer of the polymerization initiator may be any compound that can decompose the used polymerization initiator. For example, at least one selected from the group consisting of sulfites, bisulfites, bromates, diimines, diimine salts, oxalic acid, oxalates, copper salts, and iron salts is preferred. Examples of the sulfite include sodium sulfite and ammonium sulfite. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate. From the viewpoint of moderately reducing the standard specific gravity, the addition amount of the decomposer is preferably an amount corresponding to 3 to 500% (molar basis) of the initiator concentration. A more preferable lower limit is 10% (molar basis), and even more preferably 15% (molar basis). A more preferable upper limit is 400% (molar basis), and even more preferably 300% (molar basis).

[0438] The above emulsion polymerization may be carried out in the presence of 5 to 500 ppm of dicarboxylic acid with respect to the aqueous medium in order to reduce the amount of coagulum generated during the polymerization, and it is preferably carried out in the presence of 10 to 200 ppm of dicarboxylic acid. If the above dicarboxylic acid is too little with respect to the aqueous medium, there is a risk that sufficient effects cannot be obtained. If it is too much, a chain transfer reaction may occur, and the resulting polymer may have a low molecular weight. More preferably, the above dicarboxylic acid is 150 ppm or less. The above dicarboxylic acid may be added before the start of the polymerization reaction or during the polymerization.

[0439] As the above dicarboxylic acid, for example, those represented by the general formula: HOOCRCOOH (wherein R represents an alkylene group having 1 to 5 carbon atoms) are preferred, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid are more preferred, and succinic acid is even more preferred.

[0440] In the above emulsion polymerization, the polymerization temperature and polymerization pressure are appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, and the reaction rate. Usually, the polymerization temperature is 5 to 150 °C, preferably 10 °C or higher, more preferably 30 °C or higher, and even more preferably 50 °C or higher. Also, more preferably, it is 120 °C or lower, and even more preferably 100 °C or lower. The polymerization pressure is 0.05 to 10 MPaG. More preferably, the polymerization pressure is 0.3 MPaG or higher, and even more preferably 0.5 MPaG or higher. Also, more preferably, it is 5.0 MPaG or lower, and even more preferably 3.0 MPaG or lower.

[0441] When VDF is used as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the VDF concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.001 mol% or more, and more preferably 0.01 mol% or more. The above concentration may be 15 mol% or less, preferably 6.0 mol% or less, more preferably 5.0 mol% or less, even more preferably 3.0 mol% or less, and particularly preferably 1.0 mol% or less. The above VDF concentration may be maintained until the end of the polymerization reaction, or pressure reduction may be carried out during the process. VDF is preferably charged all at once before the start of polymerization, but a part thereof may be added continuously or intermittently after the start of polymerization.

[0442] When VDF is used as the modified monomer, in the above emulsion polymerization, after VDF is charged into the polymerization vessel, it is preferable not to perform pressure reduction until the polymerization is completed. Thereby, VDF can be left in the system until the end of polymerization, and the strength of the composite sheet using the obtained TFE-based polymer can be further increased.

[0443] When HFP is used as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the HFP concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.01 to 3.0 mol%. Further, when 40% by mass of all the TFE consumed in the polymerization reaction is polymerized, the HFP concentration in the gas in the reactor is preferably greater than 0 mol% and 0.2 mol% or less. The above HFP concentration is preferably maintained until the end of the polymerization reaction. HFP may be charged all at once before the start of polymerization, or a part thereof may be charged before the start of polymerization and continuously or intermittently added after the start of polymerization. By allowing HFP to remain until the end of the polymerization reaction, although the strength of the composite sheet using the obtained TFE-based polymer is high, the extrusion pressure decreases.

[0444] When using HFP as the modified monomer, in the above emulsion polymerization, in terms of further improving the strength of the coating sheet using the obtained TFE-based polymer, it is preferable to depressurize before 5 to 40% by mass of the total TFE consumed in the polymerization reaction is polymerized, and then repressurize only with TFE. The above depressurization is preferably carried out so that the pressure in the reactor becomes 0.2 MPaG or less, more preferably 0.1 MPaG or less, and even more preferably 0.05 MPaG or less. Also, it is preferably carried out so that the pressure is 0.0 MPaG or more. In addition, the above depressurization and repressurization may be carried out multiple times. The depressurization may be carried out to a reduced pressure using a vacuum pump.

[0445] When using CTFE as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the CTFE concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.001 mol% or more, and more preferably 0.01 mol% or more. The above concentration is preferably 3.0 mol% or less, and more preferably 1.0 mol% or less. The above CTFE concentration may be maintained until the end of the polymerization reaction, or depressurization may be carried out during the process. CTFE is preferably charged all at once before the start of polymerization, but a part of it may be added continuously or intermittently after the start of polymerization.

[0446] When using CTFE as the modified monomer, in the above emulsion polymerization, after charging CTFE into the polymerization vessel, it is preferable not to carry out depressurization until the polymerization is completed. Thereby, CTFE can be left in the system until the end of polymerization, and the strength of the coating sheet using the obtained TFE-based polymer can be further increased.

[0447] Step (A) is also preferably Step (A2) of obtaining an aqueous dispersion of a TFE-based polymer by emulsion-polymerizing TFE in an aqueous medium in the presence of a hydrocarbon-based surfactant. When emulsion-polymerizing in the presence of a hydrocarbon-based surfactant, the above-mentioned compound (1) and compound (2) are by-produced, and the end groups of these compounds give polar groups.

[0448] The hydrocarbon surfactant preferably has a ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms of 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0449] Step (A2) preferably includes a step of performing emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of a specific hydrocarbon surfactant, and a step of continuously adding the specific hydrocarbon surfactant in the above step.

[0450] The continuous addition of a specific hydrocarbon surfactant means, for example, adding the specific hydrocarbon surfactant not all at once, but over time, without interruption or in portions. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), or a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group) to radical treatment or oxidation treatment. The above radical treatment may be any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). For example, deionized water and a hydrocarbon surfactant are added to a reactor, the reactor is sealed, the system is purged with nitrogen, the reactor is heated and pressurized, a polymerization initiator is charged, and after stirring for a certain period of time, the reactor is depressurized until it reaches atmospheric pressure and then cooled. The above oxidation treatment is a treatment in which an oxidizing agent is added to a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). Examples of the oxidizing agent include oxygen, ozone, hydrogen peroxide solution, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, and the like. By the above production method, it is possible to produce a TFE-based polymer having a molecular weight equivalent to that of a production method using a conventional fluorine-containing surfactant without using a conventional fluorine-containing surfactant.

[0451] In the above manufacturing method, in the step of continuously adding the specific hydrocarbon surfactant, it is preferable that the addition of the hydrocarbon surfactant to the aqueous medium starts when the solid content of the TFE-based polymer formed in the aqueous medium is less than 0.60% by mass. When it is 0.5% by mass or less, it is preferable that the addition of the specific hydrocarbon surfactant to the aqueous medium starts. It is more preferable that the addition of the specific hydrocarbon surfactant starts when the solid content is 0.3% by mass or less, still more preferable when it is 0.2% by mass or less, still more preferably when it is 0.1% by mass or less, and particularly preferably starts at the same time as the polymerization initiation. The solid content is the concentration with respect to the total of the aqueous medium and the TFE-based polymer.

[0452] In the step of continuously adding the specific hydrocarbon surfactant, the addition amount of the specific hydrocarbon surfactant is preferably 0.01 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.05% by mass, a still more preferable lower limit is 0.1% by mass, a more preferable upper limit is 5% by mass, and a still more preferable upper limit is 1% by mass.

[0453] In the step of performing emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of the specific hydrocarbon surfactant, it is preferable that the amount of the specific hydrocarbon surfactant is large, and it is preferably 0.0001 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If it is less than 0.0001% by mass, the dispersing power may be insufficient, and if it exceeds 10% by mass, an effect commensurate with the amount cannot be obtained, and instead, the polymerization rate may decrease or the reaction may stop. The amount of the specific hydrocarbon surfactant is appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, etc.

[0454] As the specific hydrocarbon surfactant, the formula: R-X (wherein R is a fluorine-free organic group having 1 to 2000 carbon atoms and having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), and X is -OSO3X 1 , -COOX 1 or -SO3X 1 (X 1 is H, a metal atom, NR 1 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 1 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.)) is preferable. R preferably has 500 or less carbon atoms, more preferably 100 or less carbon atoms, still more preferably 50 or less carbon atoms, and still more preferably 30 or less carbon atoms. As the specific hydrocarbon surfactant, the following formula (a):

Chemical formula

Chemical formula

[0455] The surfactant (a) will be described.

[0456] In formula (a), R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Also, when the alkyl group has 2 or more carbon atoms, the terminal of the alkyl group can also contain the carbonyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the alkyl group. In addition, when the carbon number of the above alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring and the like can be mentioned. R 1a In, a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0457] In this specification, the "carbon number" of the above alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0458] The above alkyl group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. As the monovalent organic group containing the above ester bond, a group represented by the formula: -O-C(=O)-R 101a (wherein R 101a is an alkyl group) can be mentioned. The above alkyl group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0459] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group. R 2a and R 3ais preferably, independently, a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms. R 2a and R 3a The alkylene group constituting them preferably does not contain a carbonyl group.

[0460] The hydrogen atom bonded to the carbon atom of the alkylene group may be substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102a (wherein R 102a is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0461] R 1a R 2a and R 3a have a total carbon number of 6 or more. The total carbon number is preferably 8 or more, more preferably 9 or more, still more preferably 10 or more, preferably 20 or less, more preferably 18 or less, and still more preferably 15 or less. R 1a R 2a and R 3a Any two of them may be bonded to each other to form a ring.

[0462] In formula (a), X a is H, a metal atom, NR 4a 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 4ais H or an organic group (preferably an organic group not containing fluorine). The four Rs 4a may be the same or different. The organic group in R 4a is preferably an alkyl group. R 4a is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferable. X a is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4a 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferable. Since it is even more easily soluble in water, Na, K or NH4 is still more preferable. Na or NH4 is particularly preferable. Since it is easily removable, NH4 is most preferable. When X a is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in the TFE-based polymer or the final product.

[0463] Examples of the surfactant (a) include the following surfactants. In each formula, X a is as described above.

[0464]

Chemical formula

[0465]

Chemical formula

[0466]

Chemical formula

[0467]

Chemical formula

[0468]

Chem.

[0469]

Chem.

[0470]

Chem.

[0471]

Chem.

[0472] The surfactant (a) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

[0473] Next, the surfactant (b) will be described.

[0474] In formula (b), R 1b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring etc. are mentioned. In R 1b a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0475] In this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the above heterocyclic ring.

[0476] R 1bExamples of the substituent that the alkyl group may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group, with a methyl group or an ethyl group being particularly preferred.

[0477] R 1b The alkyl group is preferably free of a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by a halogen atom, up to 50% may be substituted by a halogen atom, and up to 25% may be substituted by a halogen atom, but a non-halogenated alkyl group free of halogen atoms such as fluorine atoms and chlorine atoms is preferred. The alkyl group preferably has no substituent.

[0478] R 1b Examples include a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms that may have a substituent, with a linear or branched alkyl group having 1 to 10 carbon atoms free of a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms free of a carbonyl group being more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms without a substituent being even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms without a substituent being even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) being particularly preferred, and a methyl group (-CH3) being most preferred.

[0479] In formula (b), R 2b and R 4b are each independently H or a substituent. A plurality of R 2b and R 4b may be the same or different from each other.

[0480] R 2b and R 4bAs the above-mentioned substituent, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0481] R 2b and R 4b The above-mentioned alkyl group as such preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above-mentioned alkyl group preferably has no substituents.

[0482] R 2b and R 4b As the above-mentioned alkyl group as such, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0483] R 2b and R 4b As such, independently, H or a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is preferable, H or a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is still more preferable, and H is particularly preferable.

[0484] In formula (b), R 3b is an alkylene group having 1 to 10 carbon atoms that may have substituents. R 3bWhen multiple are present, they may be the same or different.

[0485] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0486] The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group, or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, and even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and even more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0487] R 1b , R 2b , R 3b and R 4b may be bonded to each other to form a ring, but it is preferable that they do not form a ring.

[0488] In formula (b), n is an integer of 1 or more. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, still more preferably an integer of 5 to 25, and particularly preferably an integer of 5 to 9 or 11 to 25.

[0489] In formula (b), p and q are each independently an integer of 0 or more. As p, an integer of 0 to 10 is preferable, and 0 or 1 is more preferable. As q, an integer of 0 to 10 is preferable, and an integer of 0 to 5 is more preferable.

[0490] n, p and q are preferably integers whose total is 5 or more. The total of n, p and q is more preferably an integer of 8 or more. The total of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0491] In formula (b), X b is H, a metal atom, NR 5b 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 5b is H or an organic group (preferably an organic group not containing fluorine). The four Rs 5b may be the same or different. As the organic group in R 5b , an alkyl group is preferable. As R 5b , H or an organic group having 1 to 10 carbon atoms is preferable, H or an organic group having 1 to 4 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is still more preferable. Examples of the above metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferable. X b is a metal atom or NR 5b 4 (R 5b is as described above) may be. As X b , H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5b 4 is preferable. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferable. Since it is more easily soluble in water, Na, K or NH4 is still more preferable. Na or NH4 is particularly preferable. Since it is easily removable, NH4 is most preferable. When X b is NH4, the solubility of the above surfactant in an aqueous medium is excellent, and a metal component hardly remains in the TFE-based polymer or the final product.

[0492] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-*, or -CO- (provided that -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b excluding the carbonyl group contained in -CO-B-). B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The above alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6b is preferably H or a methyl group. * indicates the side bonded to -OSO3X b in the formula.

[0493] L is preferably a single bond.

[0494] As the surfactant (b), the following formula:

Chemical formula

[0495] Examples of the surfactant (b) include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na and the like can be mentioned.

[0496] The surfactant (b) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

[0497] Next, the surfactant (c) will be described.

[0498] In formula (c), R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the above alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Further, when the above alkyl group has 2 or more carbon atoms, the above alkyl group can also contain the above carbonyl group at the end of the alkyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the above alkyl group. In addition, when the above alkyl group has 3 or more carbon atoms, it can also contain a monovalent or divalent heterocyclic ring and can also form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring and the like can be mentioned. R 1cIn this case, a divalent heterocyclic ring may be inserted between two carbon atoms, or a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0499] In addition, in this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0500] The above alkyl group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 101c (wherein R 101c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0501] In formula (c), R 2c and R 3c are each independently a single bond or a divalent linking group. R 2c and R 3c are each independently preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms. R 2c and R 3cThe above-mentioned alkylene group constituting it preferably does not contain a carbonyl group.

[0502] The above-mentioned alkylene group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the above-mentioned monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102c (In the formula, R 102c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0503] R 1c 、R 2c and R 3c have a total carbon number of 5 or more. As the total carbon number, 7 or more is preferable, 9 or more is more preferable, 20 or less is preferable, 18 or less is more preferable, and 15 or less is even more preferable. R 1c 、R 2c and R 3c Any two of them may be bonded to each other to form a ring.

[0504] In formula (c), in the formula, A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an imidazolium optionally having a substituent, a pyridinium optionally having a substituent, or a phosphonium optionally having a substituent, and R 4c is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different. ). R 4cAs the organic group in [it], an alkyl group is preferred. R 4c is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferred. X c is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4c 4, and since it is easily soluble in water, H, Na, K, Li or NH4 is more preferred, and since it is even more easily soluble in water, Na, K or NH4 is still more preferred, Na or NH4 is particularly preferred, and since it is easily removed, NH4 is most preferred. X c being NH4 makes the surfactant excellent in solubility in an aqueous medium and makes it difficult for a metal component to remain in the TFE-based polymer or the final product.

[0505] Examples of the above surfactant (c) include the following surfactants. In each formula, A c is as described above.

[0506]

Chemical formula

[0507]

Chemical formula

[0508]

Chemical formula

[0509]

Chemical formula

[0510]

Chemical formula

[0511]

Chem.

[0512]

Chem.

[0513]

Chem.

[0514] The surfactant (c) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

[0515] Next, the surfactant (d) will be described.

[0516] In formula (d), R 1d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable, and examples thereof include a furan ring and the like. In R 1d , a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the alkyl group.

[0517] In the present specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocyclic ring.

[0518] R 1dExamples of the substituent that the alkyl group may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group, with a methyl group and an ethyl group being particularly preferred.

[0519] R 1d The alkyl group preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms. However, a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms is preferred. The alkyl group preferably has no substituents.

[0520] R 1d Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents, or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents. Even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. Particularly preferred are a methyl group (-CH3) and an ethyl group (-C2H5), with a methyl group (-CH3) being most preferred.

[0521] In formula (d), R 2d and R 4d are each independently H or a substituent. A plurality of R 2d and R 4d may be the same or different from each other.

[0522] R 2d and R 4dAs the above-mentioned substituent, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0523] R 2d and R 4d As the above-mentioned alkyl group, it is preferably free of a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group free of halogen atoms such as fluorine atoms and chlorine atoms. The above-mentioned alkyl group preferably has no substituents.

[0524] R 2d and R 4d As the above-mentioned alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms free of a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms free of a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms free of a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms free of substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0525] R 2d and R 4d Independently, H or a linear or branched alkyl group having 1 to 10 carbon atoms free of a carbonyl group is preferable, H or a linear or branched alkyl group having 1 to 3 carbon atoms free of substituents is more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is still more preferable, and H is particularly preferable.

[0526] In formula (d), R 3d is an alkylene group having 1 to 10 carbon atoms which may have substituents. R 3dWhen multiple are present, they may be the same or different.

[0527] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0528] The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group, or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, and even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and even more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0529] R 1d , R 2d , R 3d and R 4d Any two of them may be bonded to each other to form a ring.

[0530] In formula (d), n is an integer of 1 or more. As n, an integer of 1 to 40 is preferable, an integer of 1 to 30 is more preferable, and an integer of 5 to 25 is even more preferable.

[0531] In formula (d), p and q are independently an integer of 0 or more. p is preferably an integer of 0 to 10, and more preferably 0 or 1. q is preferably an integer of 0 to 10, and more preferably an integer of 0 to 5.

[0532] n, p, and q are preferably integers with a total of 6 or more. More preferably, the total of n, p, and q is an integer of 8 or more. The total of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0533] In formula (d), A d is -SO3X d or -COOX d (X d is H, a metal atom, NR 5d 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 5d is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different.) R 5d The organic group for R is preferably an alkyl group. R 5d is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred. X d is a metal atom or NR 5d 4 (R 5d is as described above). X d is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5d 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferred. Since it is even more easily soluble in water, Na, K or NH4 is still more preferred. Na or NH4 is particularly preferred. Since it is easily removed, NH4 is most preferred. X d When X is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in the TFE-based polymer or the final product.

[0534] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d-B-*, -NR 6d CO-B-*, or -CO- (however, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d excluding the carbonyl group contained in CO-B-.), where B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The above alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6d is more preferably H or a methyl group. * indicates the side bonded to A in the formula d .

[0535] L is preferably a single bond.

[0536] Examples of the above surfactant (d) include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK,[[]] CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa,[[]] CH3C(O)CH2CH2CH2CH2CH2CH2COONa,[[]] CH3C(O)CH2CH2CH2CH2CH2COONa,[[]] CH3C(O)CH2CH2CH2CH2COONa,[[]] CH3C(O)CH2CH2CH2COONa,[[]] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa,[[]] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa,[[]] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,[[]] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,[[]] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,[[]] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2SO3Na, CH3C(O)CH2CH2SO3Na, CH3C(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na etc. can be mentioned.

[0537] Surfactant (d) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

[0538] Next, surfactant (e) will be described.

[0539] In formula (e), R 1e ~R 5e represents H or a monovalent substituent, provided that at least one of R 1e and R 3e is a group represented by the general formula: -Y e -R 6e , at least one of R 2e and R 5e is a group represented by the general formula: -X e -A e , or a group represented by the general formula: -Y e -R 6e . Any two of R 1e ~R 5e may be bonded to each other to form a ring.

[0540] R 1eThe substituents that the alkyl group may have preferably include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group, and particularly preferably include a methyl group and an ethyl group.

[0541] R 1e The alkyl group preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The alkyl group preferably has no substituents.

[0542] R 1e Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group, still more preferably a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents, even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0543] Examples of the monovalent substituent include a group represented by the general formula: -Y e -R 6e a group represented by the general formula: -X e -A e a group represented by, -H, an alkyl group of C 1-20 which may have substituents, -NH2, -NHR 9e (R 9e is an organic group (preferably an organic group that does not contain fluorine)), -OH, -COOR 9e (R 9eis an organic group (preferably an organic group not containing fluorine) or -OR 9e (R 9e is preferably an organic group (preferably an organic group not containing fluorine). The number of carbon atoms of the alkyl group is preferably 1 to 10.

[0544] R 9e As 1-10 the alkyl group of 1-10 or the alkylcarbonyl group of 1-4 is preferred, and the alkyl group of 1-4 or the alkylcarbonyl group of

[0545] In the formula, X e represents, in each occurrence, the same or different divalent linking group or a bond. R 6e When it does not contain any of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X e is preferably a divalent linking group containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0546] X e As 8e - and -NR 8e CO- is preferably a divalent linking group containing at least one bond selected from the group consisting of, an alkylene group of 1-10 or a bond. R 8e represents H or an organic group (preferably an organic group not containing fluorine).

[0547] R 8e The organic group in 8e is preferably an alkyl group. R 1-10 As 1-4 the organic group of 1-4 is preferably H or an organic group of

[0548] In formula (e), A e is, in each occurrence, the same or different, -COOM e , -SO3M e or -OSO3M e (M e is H, a metal atom, NR 7e 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, R 7e is H or an organic group (preferably an organic group not containing fluorine). The four Rs 7e may be the same or different.). In formula (e), A e being -COOM e is one of the preferred embodiments.

[0549] As the organic group in R 7e , an alkyl group is preferred. As R 7e , H or an organic group of C 1-10 is preferred, H or an organic group of C 1-4 is more preferred, and H or an alkyl group of C 1-4 is even more preferred. Examples of the above metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.

[0550] As M e , H, a metal atom or NR 7e 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7e 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, Na, K or NH4 is even more preferably, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0551] In formula (e), Y e is, in each occurrence, the same or different, a divalent linking group selected from the group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e -, and -NR 8e CO-, or a bond, R 8erepresents H or an organic group (preferably an organic group not containing fluorine).

[0552] Y e is preferably a divalent linking group selected from the group consisting of a bond, -O-, -COO-, -OCO-, -CONR 8e -, and -NR 8e -CO-, and more preferably a divalent linking group selected from the group consisting of a bond, -COO- and -OCO-.

[0553] R 8e The organic group in is preferably an alkyl group. R 8e is preferably H or an organic group of C 1-10 is more preferably H or an organic group of C 1-4 is still more preferably H or an organic group of C 1-4 and still more preferably H.

[0554] In formula (e), R 6e represents, in each occurrence, the same or different, an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms. The above R 6e The organic group (preferably an organic group not containing fluorine) preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

[0555] R 6e The alkyl group of may contain one or more selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms, but does not contain these groups at the terminal of the alkyl group. The above R 6e The alkyl group of may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0556] R 6e is as follows General formula: -R 10e -CO-R 11e a group represented by General formula: -R 10e -COO-R 11e a group represented by General formula: -R 11e a group represented by General formula: -R 10e -NR 8e CO-R 11e a group represented by, or General formula: -R 10e -CONR 8e -R 11e a group represented by (In the formula, R 8e represents H or an organic group (preferably an organic group not containing fluorine). R 10e is an alkylene group, R 11e is an alkyl group which may have a substituent) is preferred. R 6e As R 10e -CO-R 11e a group represented by is more preferred.

[0557] R 8e As the organic group in, an alkyl group is preferred. R 8e As R 1-10 H or a C 1-4 organic group is preferred, H or a C 1-4 organic group is more preferred, H or a C

[0558] R 10e The number of carbon atoms of the alkylene group of is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. Also, the number of carbon atoms of the alkylene group of R 10e is preferably 1 to 20, more preferably 1 to 10, and still more preferably 3 to 10.

[0559] R 11eThe number of carbon atoms of the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, still more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 6, still more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. Also, the above R 11e The alkyl group preferably consists of only primary carbon, secondary carbon, and tertiary carbon, and particularly preferably consists of only primary carbon and secondary carbon. That is, R 11e Preferably includes methyl group, ethyl group, n-propyl group, isopropyl group, and particularly preferably methyl group.

[0560] In formula (e), at least one of R 2e and R 5e is a group represented by the general formula: -X e -A e wherein the A e being -COOM e is also one of the preferred embodiments.

[0561] As the surfactant (e), a compound represented by the general formula (e-1), a compound represented by the general formula (e-2), or a compound represented by the general formula (e-3) is preferred, and a compound represented by the general formula (e-1) or a compound represented by the general formula (e-2) is more preferred.

[0562] General formula (e-1):

Chemical formula

[0563] General formula (e-2):

Chemical formula

[0564] General formula (e-3): [Chemical formula] (In the formula, R 2e , R 4e ~R 6e , X e , A e and Y e are as described above.)

[0565] General formula: -X e -A e Examples of the group represented by are -COOM e , -R 12e COOM e , -SO3M e , -OSO3M e , -R 12e SO3M e , -R 12e OSO3M e , -OCO-R 12e -COOM e , -OCO-R 12e -SO3M e , -OCO-R 12e -OSO3M e , -COO-R 12e -COOM e , -COO-R 12e -SO3M e , -COO-R 12e -OSO3M e , -CONR 8e -R 12e -COOM e , -CONR 8e -R 12e -SO3M e , -CONR 8e -R 12e -OSO3M e , -NR 8e CO-R 12e -COOM e , -NR 8e CO-R 12e -SO3M e , -NR 8e CO-R 12e -OSO3M e , -OS(=O)2-R 12e -COOM e , -OS(=O)2-R 12e -SO3M e or -OS(=O)2-R 12e -OSO3M e (In the formula, R 8e and M e As stated above. R 12e is C 1-10 An alkylene group represented by the formula: is preferred. Above R 12e The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0566] General formula:-Y e -R 6e As the group represented by the formula: General formula:-R 10e -CO-R 11e A group represented by the formula: General formula:-OCO-R 10e -CO-R 11e A group represented by the formula: General formula:-COO-R 10e -CO-R 11e A group represented by the formula: General formula:-OCO-R 10e-COO-R 11e a group represented by General formula: -COO-R 11e a group represented by General formula: -NR 8e CO-R 10e -CO-R 11e a group represented by, or General formula: -CONR 8e -R 10e -NR 8e CO-R 11e a group represented by (wherein, R 8e , R 10e and R 11e are as described above.) is preferred.

[0567] In the formula, R 4e and R 5e are each independently preferably H or an alkyl group of C 1-4 . The above R 4e and R 5e alkyl groups may have up to 75% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, up to 50% substituted by halogen atoms, or up to 25% substituted by halogen atoms, but are preferably non-halogenated alkyl groups not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0568] As R 3e in general formula (e-1), H or an optionally substituted alkyl group of C 1-20 is preferred, an alkyl group of C 1-20 without substituents is more preferred, and H is even more preferred. The above R 3e alkyl groups may have up to 75% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, up to 50% substituted by halogen atoms, or up to 25% substituted by halogen atoms, but are preferably non-halogenated alkyl groups not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0569] R in the general formula (e-3) 2e is preferably H, OH, or an optionally substituted C 1-20 alkyl group, more preferably H, OH, or an unsubstituted C 1-20 alkyl group, and even more preferably H or OH. The above-mentioned R 2e alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0570] The surfactant (e) can be produced by a known production method.

[0571] The above-mentioned specific hydrocarbon surfactant is also preferably a carboxylic acid type hydrocarbon surfactant. The above-mentioned carboxylic acid type hydrocarbon surfactant is not limited as long as it has a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation (for example, a metal atom, ammonium, etc.). For example, from the above-mentioned specific hydrocarbon surfactants, a hydrocarbon surfactant having a carboxyl group or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation can be used. The above-mentioned carboxylic acid type hydrocarbon surfactant preferably has 50% or less of the hydrogen atoms bonded to the carbon atoms substituted by fluorine atoms, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (not substituted by fluorine atoms at all).

[0572] As the above-mentioned carboxylic acid type hydrocarbon surfactant, preferably, at least one selected from the group consisting of the surfactant (c) represented by the above formula (c) and the surfactant (d) represented by the above formula (d), and having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation (for example, a metal atom, ammonium, etc.) is preferred.

[0573] It is also preferable that the specific hydrocarbon surfactant is a sulfonic acid type hydrocarbon surfactant. The sulfonic acid type hydrocarbon surfactant is not limited as long as it has a -SO3H group, -OSO3H group, or a group in which a hydrogen atom of these groups is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.). For example, among the specific hydrocarbon surfactants described above, a hydrocarbon surfactant having a -SO3H group, -OSO3H group, or a group in which a hydrogen atom of these groups is substituted with an inorganic cation can be used. It is preferable that the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the sulfonic acid type hydrocarbon surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0574] The TFE-based polymer composition of the present disclosure can be efficiently produced by using at least one of the specific hydrocarbon surfactants. Further, the TFE-based polymer composition of the present disclosure may be produced by simultaneously using two or more of the specific hydrocarbon surfactants, or may be produced by simultaneously using a compound having other surfactant properties other than the specific hydrocarbon surfactant as long as it has volatility or can remain in a molded article made of a TFE-based polymer or the like.

[0575] As the compound having other surfactant properties, for example, those described in JP-T-2013-542308, JP-T-2013-542309, JP-T-2013-542310, etc. can be used.

[0576] The compound having other surfactant properties may be a surfactant having a hydrophilic moiety and a hydrophobic moiety on the same molecule, for example, a hydrocarbon surfactant. These may be cationic, nonionic or anionic. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above compound is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0577] Cationic surfactants usually have a positively charged hydrophilic moiety such as alkylated ammonium bromide and other alkylated ammonium halides, and a hydrophobic moiety such as long-chain fatty acids. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above cationic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0578] Anionic surfactants usually have a hydrophilic moiety such as carboxylate, sulfonate or sulfate, and a hydrophobic moiety which is a long-chain hydrocarbon moiety such as alkyl. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above anionic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0579] Nonionic surfactants usually do not contain a charged group and have a hydrophobic moiety which is a long-chain hydrocarbon. The hydrophilic moiety of nonionic surfactants contains water-soluble functional groups such as chains of ethylene ethers derived from polymerization with ethylene oxide. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above nonionic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0580] Examples of nonionic surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

[0581] Specific examples of polyoxyethylene alkyl ethers: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, etc.

[0582] Specific examples of polyoxyethylene alkyl phenyl ethers: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, etc.

[0583] Specific examples of polyoxyethylene alkyl esters: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, etc.

[0584] Specific examples of sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.

[0585] Specific examples of polyoxyethylene sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, etc.

[0586] Specific examples of glycerol esters: glycerol monomyristate, glycerol monostearate, glycerol monooleate, etc.

[0587] Specific examples of the above derivatives: polyoxyethylene alkyl amines, polyoxyethylene alkyl phenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, etc.

[0588] The above-mentioned ether and ester may have an HLB value of 10 to 18.

[0589] Examples of nonionic surfactants include Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol (registered trademark) L series manufactured by Dow Chemical Company; Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)), Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10, etc.) manufactured by BASF.

[0590] Examples of anionic hydrocarbon surfactants include Versatic (registered trademark) 10 manufactured by Resolution Performance Products, Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0591] Other compounds having surfactant properties include R-L-M (wherein R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when having 3 or more carbon atoms, may contain a monovalent or divalent heterocyclic ring or may form a ring; L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group (preferably an organic group not containing fluorine), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an arylsulfonate.). Anionic surfactants represented by the formula are also included. R5 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Specifically, those represented by CH3-(CH2) n -L-M (wherein n is an integer of 6 to 17. L and M are the same as above) can be mentioned. Mixtures in which R is an alkyl group having 12 to 16 carbon atoms and L-M is a sulfate or sodium dodecyl sulfate (SDS) can also be used. As other compounds having surfactant properties, R 6 (-L-M)2 (wherein R 6 is a linear or branched alkylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR 5 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent, R 5 is H or an organic group (preferably an organic group not containing fluorine), -ArSO3 - is an arylsulfonate. ) Also includes anionic surfactants represented by. As other compounds having surfactant properties, R 7 (-L-M)3 (wherein R 7 is a linear or branched alkylidine group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylidine group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR5 4. An optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, R 5 is H or an organic group (preferably an organic group not containing fluorine). -ArSO3 - is an arylsulfonate. An anionic surfactant represented by () is also included.

[0592] Examples of siloxane hydrocarbon surfactants include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of siloxane surfactants includes a distinct hydrophobic part and a hydrophilic part. The hydrophobic part contains one or more dihydrocarbylsiloxane units, where the substituents on the silicone atoms are completely hydrocarbons. In the sense that when the carbon atoms of the hydrocarbyl groups can be substituted by halogens such as fluorine and are completely substituted by hydrogen atoms, these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituents on the carbon atoms of the hydrocarbyl groups are hydrogen. It is preferable that the proportion of the hydrogen atoms bonded to the carbon atoms in the above siloxane surfactant substituted by fluorine atoms is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted by fluorine atoms at all).

[0593] Siloxane hydrocarbon surfactants are also disclosed in U.S. Patent No. 6,841,616.

[0594] Examples of siloxane-based anionic hydrocarbon surfactants include SilSense TM PE-100 silicone, SilSense TM CA-1 silicone, etc.

[0595] Examples of anionic hydrocarbon surfactants include sulfosuccinate surfactants such as Lankropol® K8300 manufactured by Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate surfactants include diisodecyl Na sulfosuccinate (Emulsogen® SB10 manufactured by Clariant), diisotridecyl Na sulfosuccinate (Polirol® TR / LNA manufactured by Cesapinia Chemicals), and the like.

[0596] Examples of other compounds having surfactant properties include PolyFox® surfactants (PolyFox TM PF-156A, PolyFox TM PF-136A, etc.) manufactured by Omnova Solutions, Inc.

[0597] Other compounds having surfactant properties are preferably anionic hydrocarbon surfactants. As the anionic hydrocarbon surfactants, those described above can be adopted. For example, the following hydrocarbon surfactants can be preferably adopted.

[0598] Examples of the above anionic hydrocarbon surfactants include, for example, the following formula (α): R 100 -COOM (α) (In the formula, R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4, an imidazolium optionally having a substituent, a pyridinium optionally having a substituent, or a phosphonium optionally having a substituent, and R 101 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.) The compound (α) represented by the formula is exemplified. As the organic group of R 101 , an alkyl group is preferable. R 101is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surface activity, R 100 preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms. Also, from the viewpoint of water solubility, R 100 preferably has 29 or less carbon atoms, more preferably 23 or less carbon atoms. Examples of the metal atom of M include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferable. As M, H, a metal atom or NR 101 4 is preferable, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 101 4 is more preferable, H, Na, K, Li or NH4 is still more preferable, Na, K or NH4 is still more preferably, Na or NH4 is particularly preferable, and NH4 is most preferable.

[0599] Examples of the above compound (α) include R 102 -COOM (wherein R 102 is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the carbon number is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. M is the same as above.). Also included are anionic surfactants represented by Specifically, those represented by CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28. M is the same as above) are included.

[0600] The above compound (α) may not contain a carbonyl group (excluding the carbonyl group in the carboxyl group) from the viewpoint of emulsion stability. Examples of the hydrocarbon-containing surfactant not containing the above carbonyl group include, for example, the following formula (A1): R 103-COO-M (A1) (In the formula, R 103 is an alkyl group, alkenyl group, alkylene group or alkenylene group containing 6 to 17 carbon atoms, and these may contain an ether bond. M is H, a metal atom, NR 101 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. R 101 is the same or different and is H or an organic group (preferably an organic group not containing fluorine).) Compounds are preferably exemplified. In the above formula (A1), R 103 is preferably an alkyl group or an alkenyl group (these may contain an ether group). The alkyl group or alkenyl group in the above R 103 may be linear or branched. The number of carbon atoms in the above R 103 is not limited, but is, for example, 2 to 29.

[0601] When the above alkyl group is linear, the number of carbon atoms in R 103 is preferably 3 to 29, and more preferably 5 to 23. When the above alkyl group is branched, the number of carbon atoms in R 103 is preferably 5 to 35, and more preferably 11 to 23. When the above alkenyl group is linear, the number of carbon atoms in R 103 is preferably 2 to 29, and more preferably 9 to 23. When the above alkenyl group is branched, the number of carbon atoms in R 103 is preferably 2 to 29, and more preferably 9 to 23.

[0602] Examples of the above alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, a vinyl group and the like.

[0603] Examples of the above compound (α) include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, osbond acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid, and salts thereof. Particularly, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof is preferable. Examples of the above salt include those in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 11 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, but are not particularly limited.

[0604] Examples of the above anionic hydrocarbon surfactant also include, for example, the following formula (β): R 100 -SO3M (β) (In the formula, R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 101is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different. The compound (β) represented by ) is also included. R 101 As the organic group, an alkyl group is preferred. R 101 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant properties, R 100 preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms. Also, from the viewpoint of water solubility, R 100 preferably has 29 or fewer carbon atoms, more preferably 23 or fewer carbon atoms. Examples of the metal atom of M include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K, or Li is preferred. As M, H, a metal atom, or NR 101 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 101 4 is more preferred, H, Na, K, Li, or NH4 is still more preferred, Na, K, or NH4 is still more preferably, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0605] Examples of the compound (β) include R 102 -SO3M (wherein R 102 is a linear or branched alkyl group, alkenyl group, alkylene group, or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group, or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When having 3 or more carbon atoms, they may contain a monovalent or divalent heterocyclic ring or may form a ring. M is the same as above.). The anionic surfactant represented by this formula is also included. Specifically, those represented by CH3-(CH2) n -SO3M (wherein n is an integer of 2 to 28. M is the same as above) are included.

[0606] From the viewpoint of emulsion stability, the above compound (β) may not contain a carbonyl group (excluding the carbonyl group in the carboxyl group). Examples of the hydrocarbon-containing surfactant that does not contain the above carbonyl group include, for example, the following formula (B1): R 103 -SO3-M (B1) (In the formula, R 103 is an alkyl group, alkenyl group, alkylene group or alkenylene group containing 6 to 17 carbon atoms, and these may contain an ether bond. M is H, a metal atom, NR 101 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. R 101 is the same or different and is H or an organic group (preferably an organic group not containing fluorine).) Compounds are preferably exemplified. In the above formula (B), R 103 is preferably an alkyl group or an alkenyl group (these may contain an ether group). The alkyl group or alkenyl group in the above R 103 may be linear or branched. The number of carbon atoms in the above R 103 is not limited, but is, for example, 2 to 29.

[0607] When the above alkyl group is linear, the number of carbon atoms in R 103 is preferably 3 to 29, and more preferably 5 to 23. When the above alkyl group is branched, the number of carbon atoms in R 103 is preferably 5 to 35, and more preferably 11 to 23. When the above alkenyl group is linear, the number of carbon atoms in R 103 is preferably 2 to 29, and more preferably 9 to 23. When the above alkenyl group is branched, the number of carbon atoms in R 103 is preferably 2 to 29, and more preferably 9 to 23.

[0608] Examples of the above alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, a vinyl group and the like.

[0609] Examples of the above compound (β) include sulfonic acids such as aliphatic, unsaturated aliphatic, and aromatic sulfonic acids, sulfuric acid esters such as aliphatic, unsaturated aliphatic, and aromatic sulfuric acid esters, and salts thereof. Examples of the above sulfonic acid include 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, perfluorobutanesulfonic acid, linear alkylbenzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, DBS, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, butylnaphthalenesulfonic acid. Examples of the above sulfuric acid ester include sodium alkyl sulfate, α-sulfo fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, α-olefin sulfonate, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid. As the above compound (β), at least one selected from the group consisting of saturated aliphatic and aromatic sulfuric acid esters and salts thereof is particularly preferable, and at least one selected from the group consisting of sodium alkyl sulfate, α-sulfo fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, α-olefin sulfonate, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid, and salts thereof is more preferable. Examples of the above salt include those in which the hydrogen of the sulfonic acid group is a metal atom of the above formula M, NR 11 4, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, but are not particularly limited.

[0610] Examples of the above anionic hydrocarbon surfactant include the following formula (1-0A): [Chemical formula] (In the formula, R 1A ~R 5A is H, a monovalent hydrocarbon group which may contain an ester group between carbon-carbon atoms, or a group represented by the general formula: -X A -A. However, at least one of R 2A and R 5A represents a group represented by the general formula: -X A -A.) X A is, in each occurrence, the same or different, a divalent hydrocarbon group, or a bond; A is, in each occurrence, the same or different, -COOM (M is H, a metal atom, NR 7 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group (preferably an organic group not containing fluorine)); R 1A ~R 5A Among them, any two of them may be bonded to each other to form a ring. ) And the like, such as the surfactant (1-0A) represented by the formula.

[0611] In the general formula (1-0A), R 1A ~R 5A In, the carbon number of the monovalent hydrocarbon group which may contain an ester group between carbon-carbon atoms is preferably 1 to 50, and more preferably 5 to 20. R 1A ~R 5A Among them, any two of them may be bonded to each other to form a ring. As the above-mentioned monovalent hydrocarbon group which may contain an ester group between carbon-carbon atoms, an alkyl group is preferable. In the formula, X A In, the carbon number of the divalent hydrocarbon group is preferably 1 to 50, and more preferably 5 to 20. Examples of the above divalent hydrocarbon group include an alkylene group and an alkanediyl group, and an alkylene group is preferable.

[0612] In the general formula (1-0A), R2A and R 5A any one of them is preferably a group represented by the above general formula: -X A -A, and it is more preferable that R 2A is a group represented by the above general formula: -X A -A.

[0613] In the general formula (1-0A), as a preferred embodiment, R 2A is a group represented by the general formula: -X A -A, and R 1A , R 3A , R 4A and R 5A are H. In this case, X A is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0614] In the general formula (1-0A), as another preferred embodiment, R 2A is a group represented by the general formula: -X A -A, and R 1A and R 3A are groups represented by -Y A -R 6 , Y A is the same or different in each occurrence and is -COO-, -OCO-, or a bond, and R 6 is the same or different in each occurrence and is an alkyl group having 2 or more carbon atoms. In this case, it is preferable that R 4A and R 5A are H.

[0615] Examples of the hydrocarbon surfactant represented by the general formula (1-0A) include glutaric acid or its salt, adipic acid or its salt, pimelic acid or its salt, suberic acid or its salt, azelaic acid or its salt, sebacic acid or its salt, and the like. In addition, the aliphatic carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) may be a two-chain and two-hydrophilic group type synthetic surfactant. For example, as gemini surfactants, Gemini SA-F (Chukyo Yushi Co., Ltd.), Gemsurf α142 (dodecyl group with 12 carbon atoms), Gemsurf α102 (with 10 carbon atoms), Gemsurf α182 (with 14 carbon atoms), etc. can be mentioned.

[0616] As the above anionic hydrocarbon surfactant, the following formula I: R-(XZ) n (I) (In the formula, R is a hydrophobic hydrocarbon moiety containing one or more saturated or unsaturated, acyclic or cyclic aliphatic groups. The percentage of the total number of CH3 groups with respect to the total of CH3, CH2, and CH groups in one or more aliphatic groups is at least about 70%, and the hydrophobic moiety does not contain siloxane units. Each X may be the same or different and represents an ionic hydrophilic moiety. Each Z may be the same or different and represents one or more counterions of the ionic hydrophilic moiety. n is 1 to 3.) Compound I represented by this is also included.

[0617] Compound I shows low reactivity with polymerization initiators and / or growing fluoropolymer radicals in the emulsion polymerization of fluoromonomers.

[0618] Compound I has the following formula:

Chemical formula

[0619] Compound I has the following formula II:

Chemical formula

[0620] As the compound II, for example, the following compounds are preferred. [Chemical formula] Y in the above formula + may be hydrogen, ammonium, or an alkali metal.

[0621] Compound I has the following formula III: [Chemical formula] (In the formula, R 3 , R 4’ , and R 4’’ are the same or different and are hydrogen or a saturated or unsaturated, acyclic or cyclic aliphatic group having 4 to 16 carbon atoms, and R 3 , R 4’ , and R 4’’ the percentage of the total of CH3 in relation to the total of CH3, CH2 and CH groups in the group is at least about 70%. However, 3 , R 4’ , and R 4’’ at least one of them is not hydrogen, and when R 4’ and R 4’’ are hydrogen, R3 is not hydrogen, but R 3 is hydrogen, R 4’ and R 4’’ are not hydrogen. Y + is hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal, or alkaline earth metal. It is also preferable that it is Compound III represented by).

[0622] As Compound III, for example, the following compounds are preferable.

Chemical formula

[0623] Even when the above specific hydrocarbon surfactant is not used, the TFE-based polymer composition of the present disclosure is obtained by a production method including a polymerization step of polymerizing only tetrafluoroethylene or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium having a pH of 4.0 or more in the presence of a hydrocarbon surfactant and a polymerization initiator. Conventionally, since a polymerization initiator showing acidity has been used in the polymerization step for producing a TFE-based polymer, the pH of the aqueous medium used in the polymerization was less than 4.0. As a result of intensive studies by the present inventors, it was unexpectedly found that by setting the pH of the aqueous medium used in the polymerization to 4.0 or more, the stability of the polymerization is improved and a TFE-based polymer having a high molecular weight can be produced. The above manufacturing method involves polymerizing only tetrafluoroethylene or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium having a pH of 4.0 or higher. The pH may be 4.0 or higher, preferably more than 4.0, more preferably 4.5 or higher, still more preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, especially preferably 6.5 or higher, particularly preferably 7.0 or higher, particularly preferably 7.5 or higher, and particularly preferably 8.0 or higher. The upper limit of the pH is not particularly limited, and for example, it may be 13.0 or lower. From the perspective of corrosion of the polymerization tank, it is preferably 12.0 or lower, more preferably 11.5 or lower, and even more preferably 11.0 or lower. The above pH can be measured using a pH meter.

[0624] In the above manufacturing method, the method for adjusting the pH of the aqueous medium to 4.0 or higher is not limited. For example, the pH can be adjusted to 4.0 or higher by using an alkaline aqueous solution, an aqueous dispersion showing alkalinity, or a pH adjuster, but it is not particularly limited. Also, even when using a polymerization initiator that shows acidity when dissolved in the aqueous medium, the pH can be adjusted to 4.0 or higher by further adding an alkaline compound such as sodium hydroxide. The above alkaline compound may be a compound that dissolves in water and ionizes to produce OH - Any compound that can do s...

Claims

1. A tetrafluoroethylene-based polymer composition for use in a binder for an electrochemical device, the tetrafluoroethylene-based polymer composition having a polar group, a content of the polar group being less than 0.020 meq / g based on the tetrafluoroethylene-based polymer composition, the tetrafluoroethylene-based polymer composition being non-melt processable, and having an apparent density of less than 0.50 g / ml.

2. 2. The tetrafluoroethylene polymer composition according to claim 1, having an apparent density of 0.35 g / ml or more and less than 0.50 g / ml.

3. 3. The tetrafluoroethylene polymer composition according to claim 1 or 2, which is used as a binder for lithium ion secondary batteries and is in the form of a powder.

4. A binder for electrochemical devices consisting essentially of a tetrafluoroethylene-based polymer composition, the tetrafluoroethylene-based polymer composition having a polar group, a content of the polar group being less than 0.020 meq / g relative to the tetrafluoroethylene-based polymer composition, the binder being non-melt processable, and having an apparent density of less than 0.50 g / ml.

5. 5. The binder for electrochemical devices according to claim 4, wherein the tetrafluoroethylene polymer composition has an apparent density of 0.35 g / ml or more and less than 0.50 g / ml.

6. 6. The binder for electrochemical devices according to claim 4, wherein the polar group is at least one functional group selected from the group consisting of an amino group, a nitrile group, and an oxygen-containing polar group.

7. The oxygen-containing polar group is a carbonyl group-containing group, an epoxy group, an oxetanyl group, or —SO ３ X ａ , -SO ２ X ａ , -OSO ２ X ａ , -PO ３ X ａ , and -OX ａ (In the formula, X ａ is -H, a metal atom, -NR １ ４ , an imidazolium group which may have a substituent, a pyridinium group which may have a substituent, a phosphonium group which may have a substituent, an alkyl group, or a nitrile group. １ 7. The binder for electrochemical devices according to claim 6, wherein R is H or an organic group.

8. 6. The binder for electrochemical devices according to claim 4, wherein the tetrafluoroethylene polymer is a copolymer of tetrafluoroethylene and a monomer having a polar group.

9. 6. The binder for electrochemical devices according to claim 4, wherein the tetrafluoroethylene polymer composition contains a fluorine-containing compound having a hydrophilic group.

10. The hydrophilic group is -SO ３ M ａ , -SO ２ M ａ , -OSO ２ M ａ , -PO ３ M ａ , -COOM ａ , -OCOM ａ , and -O.M. ａ (In the formula, M ａ is -H, a metal atom, -NR １ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium; R １ 10. The binder for electrochemical devices according to claim 9, wherein the binder is at least one selected from the group consisting of:

11. The fluorine-containing compound having a hydrophilic group is represented by the following general formula (N ０ ): X ｎ０ -Rf ｎ０ -Y ０ (N ０ ) (In the formula, X ｎ０ is H, Cl or F. ｎ０ is a linear, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H's are replaced by F, and the alkylene group may contain one or more ether bonds, and some of the H's may be replaced by Cl. ０ 10. The binder for electrochemical devices according to claim 9, which is a compound represented by the formula:

12. The binder for electrochemical devices according to claim 9, wherein the fluorine-containing compound having a hydrophilic group is at least one selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2): General formula (1): (H-(CF ２ ) ｍ－１ -COO) ｐ M １ (In the formula, m is 4 to 20. １ is H, a metal atom, NR ５ ４ (R ５ may be the same or different and are H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2. General formula (2): (H-(CF ２ ) ｎ -SO ３ ) ｑ M ２ (wherein n is 4 to 20. M ２ is H, metal atom, NR ５ ４ (R ５ is the same as above), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. q is 1 or 2.

13. 10. The binder for electrochemical devices according to claim 9, wherein the fluorine-containing compound having a hydrophilic group is a polymer compound having an ionic group.

14. The binder for electrochemical devices according to claim 13, wherein the polymer compound is at least one selected from the group consisting of a polymer (I) containing polymerization units (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II): General formula (I): CX １ X ３ =CX ２ R(-CZ １ Z ２ -A ０ ) ｍ (I) (In the formula, X １ and X ３ are each independently F, Cl, H or CF ３ and ０ is an anionic group; X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more. General formula (II): () Ｘ ︹ Ａ  ＦＡ１  ＦＡ２ ︹ Ａ ) Ｘ ' (=) (In the formula, R ＦＡ１ is -Rf １ ｐ -R Ｆ -O ｑ - and R ＦＡ２ is -Rf ２ ｐ -R ＦＸ -O ｑ - and R Ｆ is a divalent fluoropolyether group, R ＦＸ is a divalent fluoropolyether group containing an anionic group, Rf １ and Rf ２ each independently represents a C which may be substituted by one or more fluorine atoms; １－６ is an alkylene group, Each p is independently 0 or 1; Each q is independently 0 or 1; X Ａ each independently represents a single bond or a divalent to decavalent group, T Ｘ and T Ｘ Each of the C′ groups independently contains one or more of H, O, and Cl, and does not contain the anionic group. １ ~C ２４ (hydro)(fluoro)carbon groups, and (ii) at least one of said anionic groups, １ ~C ２４ (hydro)(fluoro)carbon groups.

15. 15. The binder for electrochemical devices according to claim 14, wherein the polymer compound is a polymer (I) containing polymerization units (I) based on a monomer represented by the general formula (I).

16. 6. The binder for electrochemical devices according to claim 4 or 5, which is a binder for lithium ion secondary batteries and is in the form of a powder.

17. 6. An electrode mixture comprising the tetrafluoroethylene polymer composition according to claim 1 or 2, or the binder for electrochemical devices according to claim 4 or 5, and an electrode active material.

18. The electrode mixture according to claim 17, which is in the form of a sheet.

19. 6. An electrode comprising the tetrafluoroethylene polymer composition according to claim 1 or 2, or the binder for electrochemical devices according to claim 4 or 5, an electrode active material, and a current collector.

20. A secondary battery comprising the electrode according to claim 19.

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