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 yielding a mixture sheet with excellent uniformity and to provide a binder for the electrochemical device, an electrode mixture, an electrode, and a secondary battery, all using the same.SOLUTION: A tetrafluoroethylene polymer composition is for use in a binder for an electrochemical device. The tetrafluoroethylene polymer composition has an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less.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 mixture, an electrode, and a secondary battery. [Background technology]

[0002] Secondary batteries such as lithium-ion secondary batteries have high voltage, high energy density, low self-discharge, little memory effect, and can be made extremely lightweight, and are therefore used in small, portable electrical and electronic devices such as notebook computers, mobile phones, smartphones, tablet computers, and ultrabooks, and are also being put into practical use as a wide range of power sources, including on-board power supplies for driving automobiles and large stationary power supplies. There is a demand for even higher energy densities in secondary batteries, and further improvements in their battery characteristics are also required.

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

[0004] Patent Documents 2 to 7 describe the use of polytetrafluoroethylene as a binder for batteries. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2017-517862 [Patent Document 2] International Publication No. 2021 / 181887 [Patent Document 3] International Publication No. 2021 / 192541 [Patent Document 4] International Publication No. 2022 / 138942 [Patent Document 5] International Publication No. 2022 / 138939 [Patent Document 6] International Publication No. 2022 / 024520 [Patent Document 7] International Publication No. 2023 / 098300 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present disclosure is to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device, which can give a mixture sheet with excellent uniformity, as well as a binder for an electrochemical device, an electrode mixture, an electrode, and a secondary battery using the same. [Means for solving the problem]

[0007] The present disclosure (1) is a tetrafluoroethylene-based polymer composition used as a binder for electrochemical devices, the tetrafluoroethylene-based polymer composition having an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less.

[0008] The present disclosure (2) includes a tetrafluoroethylene-based polymer, In the tetrafluoroethylene-based polymer composition according to the present disclosure (1), the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a tetrafluoroethylene homopolymer and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

[0009] The present disclosure (3) is a powder of the tetrafluoroethylene-based polymer composition according to the present disclosure (1) or (2).

[0010] The present disclosure (4) is a tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (3), which is used as a binder for lithium ion secondary batteries and is in the form of powder.

[0011] The present disclosure (5) is a binder for electrochemical devices consisting essentially of a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition has an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less.

[0012] The present disclosure (6) is directed to a method for manufacturing a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition contains a tetrafluoroethylene-based polymer, In the binder for electrochemical devices according to the present disclosure (5), the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a homopolymer of tetrafluoroethylene and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

[0013] The present disclosure (7) is the binder for electrochemical devices according to the present disclosure (5) or (6), wherein the tetrafluoroethylene-based polymer composition has an apparent density of 0.40 g / ml or less.

[0014] The present disclosure (8) is the binder for electrochemical devices according to any one of the present disclosures (5) to (7), wherein the tetrafluoroethylene-based polymer composition is non-melt-processable.

[0015] The present disclosure (9) is the binder for electrochemical devices according to any one of the present disclosures (5) to (8), wherein the tetrafluoroethylene polymer composition contains a fluorine-containing compound having a hydrophilic group.

[0016] The present disclosure (10) is the binder for electrochemical devices according to the present disclosure (9), wherein the molecular weight of the fluorine-containing compound having a hydrophilic group is 1,000 or less.

[0017] The present disclosure (11) is a method for manufacturing a compound according to the present invention, wherein the hydrophilic group is -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a, -OCOM a , and -OM a (In the formula, M a -H, metal atom, -NR 1 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 1 is H or an organic group.) is at least one selected from the group consisting of:

[0018] The present disclosure (12) is directed to a method for producing a fluorine-containing compound having a hydrophilic group, the method comprising: 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 substituted with F, and the alkylene group may contain one or more ether bonds, and some of the H's may be substituted with Cl. Y 0 is an anionic group. The binder for electrochemical devices according to any one of the present disclosures (9) to (11) is a compound represented by the formula:

[0019] The present disclosure (13) is the binder for electrochemical devices according to the present disclosure (9), wherein the fluorine-containing compound having a hydrophilic group is a polymer compound having an ionic group.

[0020] The present disclosure (14) is directed to a method for preparing a ionic group, wherein the ionic group is -SO3M a , -SO2M a , -PO3M a and -COOM a (In the formula, M a -H, metal atom, -NR 1 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 1is H or an organic group.) is at least one selected from the group consisting of:

[0021] The present disclosure (15) is the binder for electrochemical devices according to the present disclosure (13) or (14), wherein the content of the ionic group is 0.8 meq / g or more relative to the polymer compound.

[0022] The present disclosure (16) is the binder for electrochemical devices according to any one of the present disclosures (13) to (15), wherein the polymer compound has an ion exchange rate of 53 or less.

[0023] The present disclosure (17) is the binder for electrochemical devices according to any one of the present disclosures (13) to (16), 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 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 are each independently F, Cl, H, or CF; 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; and m is an integer of 1 or more. General formula (II): T X -X A -R FA1 -R FA2 -X A -T X (II) (In the formula, RFA1 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 optionally substituted by one or more fluorine atoms; 1-6 is an alkylene group, p's are each independently 0 or 1; Each q is independently 0 or 1; X A are each independently a single bond or a divalent to decavalent group, T X and T X (i) each independently represents a C1-C alkyl group which may contain one or more of H, O, and Cl and which does not have an anionic group; 24 (hydro)(fluoro)carbon groups, and (ii) a C1-C group containing at least one of said anionic groups. 24 (hydro)(fluoro)carbon groups.)

[0024] The present disclosure (18) is the binder for electrochemical devices according to the present disclosure (10) or (11), wherein the fluorine-containing compound having a hydrophilic group is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a perfluoroethercarboxylic acid (III) represented by the following general formula (III), and a polymer containing a polymerization unit (1A) based on a monomer represented by the following general formula (1A): General formula (1):(H-(CF2) m-1 -COO) p M 1 (wherein m is 4 to 20. M 1 is H, 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), 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 (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. Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III) (In the formula, 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. CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a -H, metal atom, -NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group.

[0025] The present disclosure (19) is the binder for electrochemical devices according to any one of the present disclosures (5) to (18), which is in the form of powder.

[0026] The present disclosure (20) is the binder for electrochemical devices according to any one of the present disclosures (5) to (19), which is a binder for lithium ion secondary batteries.

[0027] The present disclosure (21) is a tetrafluoroethylene-based polymer composition used as a binder for electrochemical devices, the tetrafluoroethylene-based polymer composition having an average particle size of 1 μm or more and 300 μm or less, and a proportion of particles having an aspect ratio of 3.0 or more of 15% or less.

[0028] The present disclosure (22) includes a tetrafluoroethylene-based polymer, The tetrafluoroethylene-based polymer composition according to the present disclosure (21), wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a tetrafluoroethylene homopolymer and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

[0029] The present disclosure (23) is a powder of the tetrafluoroethylene-based polymer composition according to the present disclosure (21) or (22).

[0030] The present disclosure (24) is a tetrafluoroethylene-based polymer composition according to any one of the present disclosures (21) to (23), which is used as a binder for lithium ion secondary batteries and is in the form of powder.

[0031] The present disclosure (25) is a binder for electrochemical devices consisting essentially of a tetrafluoroethylene-based polymer composition, in which the tetrafluoroethylene-based polymer composition has an average particle size of 1 μm or more and 300 μm or less, and the proportion of particles having an aspect ratio of 3.0 or more is 15% or less.

[0032] The present disclosure (26) relates to a tetrafluoroethylene-based polymer composition comprising a tetrafluoroethylene-based polymer, In the binder for electrochemical devices according to the present disclosure (25), the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a homopolymer of tetrafluoroethylene and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

[0033] The present disclosure (27) is the binder for electrochemical devices according to the present disclosure (25) or (26) in the form of powder.

[0034] The present disclosure (28) is the binder for electrochemical devices according to any one of the present disclosures (25) to (27), which is a binder for lithium ion secondary batteries.

[0035] The present disclosure (29) is an electrode mixture comprising the tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (4), (21) to (24), or the binder for electrochemical devices according to any one of the present disclosures (5) to (20), (25) to (28), and an electrode active material.

[0036] The present disclosure (30) is the electrode mixture according to the present disclosure (29) in the form of a sheet.

[0037] The present disclosure (31) is an electrode comprising the tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (4), (21) to (24), or the binder for electrochemical devices according to any one of the present disclosures (5) to (20), (25) to (28), an electrode active material, and a current collector.

[0038] The present disclosure (32) is a secondary battery including the electrode according to the present disclosure (31). [Effects of the Invention]

[0039] According to the present disclosure, it is possible to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device, which can give a mixture sheet with excellent uniformity, as well as a binder for an electrochemical device, an electrode mixture, an electrode, and a secondary battery using the same. [Brief explanation of the drawings]

[0040] [Figure 1] Schematic diagrams showing examples of cone-type impellers: (a) an upward-facing cone-type impeller, (b) a downward-facing cone-type impeller, (c) a face-to-face cone-type impeller, and (d) a double-cone-type impeller with a disk saw. DETAILED DESCRIPTION OF THE INVENTION

[0041] In this disclosure, "organic group" means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. The organic group is preferably an alkyl group which may have one or more substituents.

[0042] The present disclosure will be specifically described below.

[0043] The present disclosure provides a tetrafluoroethylene (TFE)-based polymer composition used as a binder for electrochemical devices, the TFE-based polymer composition having an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less (hereinafter also referred to as TFE-based polymer composition (1) of the present disclosure).

[0044] The present disclosure also provides a TFE-based polymer composition for use in a binder for electrochemical devices, the TFE-based polymer composition having an average particle size of 1 μm or more and 300 μm or less and a proportion of particles having an aspect ratio of 3.0 or more of 15% or less (hereinafter also referred to as TFE-based polymer composition (2) of the present disclosure).

[0045] In this specification, unless otherwise specified, the TFE-based polymer compositions (1) and (2) of the present disclosure will be collectively referred to as the "TFE-based polymer composition of the present disclosure."

[0046] The TFE polymer composition of the present disclosure, having the above-described structure, can provide a mixture sheet with excellent uniformity (with little in-plane variation) and also with excellent strength and flexibility. The TFE-based polymer composition of the present disclosure can be used in a dry process, which eliminates the need for a large amount of a dispersion medium such as water or an organic solvent, and allows for a wide selection of electrode active materials and solid electrolytes to be combined, which is advantageous in terms of production process, and also reduces the number of steps and costs associated with the use of a dispersion medium. Furthermore, the TFE polymer composition of the present disclosure has excellent binding strength with active materials and electrolytes, so that the amount used can be reduced.

[0047] The TFE polymer composition of the present disclosure has an average particle size of 1 μm or more and 300 μm or less. In order to obtain a mixture sheet with even more excellent uniformity, the average particle size is preferably 3 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, even more preferably 20 μm or more, even more preferably 30 μm or more, and is preferably 250 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, even more preferably 100 μm or less, even more preferably 70 μm or less, and even more preferably 50 μm or less. The average particle size is determined by the following laser diffraction method. It is performed in a dry state using a HELOS & RODOS system (product name, manufactured by SYMPATEC). The powder to be measured is dispersed with compressed air at a dispersion pressure of 2 bar, and the measurement sensor detects the shadow of the powder projected by a laser. The particle size distribution of the powder is calculated, and the average particle size (50% cumulative particle size) D50 is determined on a volume basis. D50 is equal to the particle size corresponding to 50% of the cumulative particle size distribution.

[0048] The TFE-based polymer composition (1) of the present disclosure has an average aspect ratio of 2.0 or less. The TFE-based polymer composition (2) of the present disclosure preferably has an average aspect ratio of 2.0 or less. In order to obtain a mixture sheet with even better uniformity, the average aspect ratio is preferably 1.9 or less, more preferably 1.8 or less, even more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, even more preferably 1.3 or less, even more preferably 1.2 or less, and particularly preferably 1.1 or less. The average aspect ratio may also be 1.0 or more. The average aspect ratio is determined by observing the TFE-based polymer composition with a scanning electron microscope (SEM), processing the images of 200 or more randomly selected particles, and averaging the ratio of their major axis to their minor axis.

[0049] In the TFE polymer composition (1) of the present disclosure, the proportion of particles having an aspect ratio of 3.0 or more is preferably 15% or less. In the TFE-based polymer composition (2) of the present disclosure, the proportion of particles having an aspect ratio of 3.0 or more is 15% or less. In order to obtain a composite sheet with even better uniformity, the proportion of particles having an aspect ratio of 3.0 or more is preferably 13% or less, more preferably 10% or less, even more preferably 8% or less, even more preferably 5% or less, and particularly preferably less than 5%, and the proportion may also be 1% or more. The above ratio is determined by observing the TFE-based polymer composition with a scanning electron microscope (SEM), processing images of 200 or more randomly selected particles, determining the aspect ratio of each particle from the ratio of its major axis to its minor axis, and calculating the ratio to the total number of the selected particles.

[0050] The TFE-based polymer composition of the present disclosure preferably has an apparent density of 0.40 g / ml or less, more preferably 0.38 g / ml or less, even more preferably 0.35 g / ml or less, even more preferably 0.33 g / ml or less, particularly preferably 0.30 g / ml or less, and preferably 0.05 g / ml or more, and also preferably 0.20 g / ml or more, in order to obtain a mixture sheet with even more excellent uniformity. The apparent density is measured in accordance with JIS K 6892.

[0051] The TFE-based polymer compositions of the present disclosure are preferably non-melt processable. In this specification, 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 0.05 g / 10 min or less, and even more preferably 0.01 g / 10 min or less. The MFR is a value obtained in accordance with ASTM D1238 using a melt indexer, as the mass (g / 10 min) of polymer flowing out of a nozzle having an inner diameter of 2.095 mm and a length of 8 mm at 372°C under a load of 5 kg per 10 min.

[0052] The TFE-based polymer composition of the present disclosure contains a TFE-based polymer. The TFE-based polymer may be a TFE homopolymer or a TFE copolymer containing polymerized units based on TFE (TFE units) and polymerized units based on a modified monomer copolymerizable with TFE (modified monomer units). The TFE-based polymer may be polytetrafluoroethylene (PTFE), which includes a TFE homopolymer 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 TFE-based polymer is preferably PTFE, and more preferably modified PTFE, in that a mixture sheet having even more excellent uniformity, strength, and flexibility can be obtained. In the present disclosure, a homopolymer of TFE refers to one in which the content of modified monomer units relative to all polymerized units is less than 0.0001% by mass.

[0053] The content of the modified monomer unit is preferably in the range of 0.0001 to 10% by mass relative to the total polymerized units, since this allows for a composite sheet with even more excellent uniformity, strength, and flexibility to be obtained. The lower limit of the content of the modified monomer unit is more preferably 0.001% by mass, even more preferably 0.010% by mass, even more preferably 0.015% by mass, and particularly preferably 0.020% by mass. The upper limit of the content of the modified monomer unit is preferably 5.0% by mass, more preferably 3.0% by mass, even more preferably 1.0% by mass, even more preferably 0.80% by mass, even more preferably 0.60% by mass, even more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, even more preferably 0.20% by mass, and particularly preferably 0.10% by mass. In this specification, the modified monomer unit means a part of the molecular structure of the TFE polymer that is derived from the modified monomer.

[0054] The content of each of the above-mentioned polymerized units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0055] The modifying monomer is not particularly limited as long as it can be copolymerized with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene (HFP); hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF); perhaloolefins such as chlorotrifluoroethylene (CTFE); perfluorovinyl ethers; perfluoroallyl ethers; (perfluoroalkyl)ethylenes, ethylenes, and monomers having polar groups. The modifying monomers used may be one type or multiple types.

[0056] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (A): CF2=CF-ORf 1 (A) (In the formula, Rf 1 represents a perfluoroorganic group. ) and perfluorounsaturated compounds represented by the following formulas are included. In this specification, the "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0057] The perfluorovinyl ether may be, for example, a compound represented by the general formula (A) in which Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0058] Examples of the perfluoroalkyl group in the PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0059] The perfluorovinyl ether further includes a compound represented by the general formula (A) in which Rf 1 is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 1 is the following formula:

[0060] [ka]

[0061] (wherein m represents 0 or an integer of 1 to 4), Rf 1 is the following formula:

[0062] [ka]

[0063] (wherein n represents an integer of 1 to 4).

[0064] The (perfluoroalkyl)ethylene [PFAE] is not particularly limited, and examples thereof include (perfluorobutyl)ethylene [PFBE] and (perfluorohexyl)ethylene.

[0065] Examples of perfluoroallyl ethers include those represented by the general formula (B): CF2=CF-CF2-ORf 2 (B) (In the formula, Rf 2 represents a perfluoroorganic group.

[0066] Above Rf 2 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms. The perfluoroallyl ether is preferably 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, more preferably 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, and even more preferably CF2=CF-CF2-O-CF2CF2CF3.

[0067] 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. 4 is F, Cl, Rf or O-Rf. Rf is a perfluoro organic group.

[0068] Rf in general formula (i) is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0069] The polar group-containing monomer may be a fluorine-free monomer or a fluorine-containing monomer.

[0070] Examples of the fluorine-free monomer include hydroxyl group-containing fluorine-free monomers such as hydroxyalkyl vinyl ethers, such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; carboxyl group-containing fluorine-free monomers, such as acrylic acid, methacrylic acid, itaconic acid, succinic acid, fumaric acid, crotonic acid, maleic acid, citraconic acid, undecylenic acid, and acetylenedicarboxylic acid; itaconic anhydride (hereinafter also referred to as "IAH"), citraconic anhydride (hereinafter also referred to as "CAH"), 5-norbornene-2, Examples of the non-fluorine-containing monomer include 3-dicarboxylic acid anhydride (hereinafter also referred to as "NAH"), succinic anhydride, fumaric anhydride, maleic anhydride, and other non-fluorine-containing monomers having an acid anhydride residue; vinyl sulfonic acid, and other non-fluorine-containing monomers having a sulfo group; glycidyl vinyl ether, glycidyl allyl ether, and other non-fluorine-containing monomers having an epoxy group (glycidyl group); aminoalkyl vinyl ether, aminoalkyl allyl ether, and other non-fluorine-containing monomers having an amino group; (meth)acrylamide, methylolacrylamide, and other non-fluorine-containing monomers having an amide group; and acrylonitrile, methacrylonitrile, and other non-fluorine-containing monomers having a nitrile group. Among these, a fluorine-free monomer having a carboxyl group and a fluorine-free monomer having an acid anhydride residue are preferred, a fluorine-free monomer having an acid anhydride residue is more preferred, and a cyclic fluorine-free monomer having an acid anhydride residue is even more preferred.

[0071] The polar group-containing monomer preferably includes a modified monomer having a functional group reactive in radical polymerization and a hydrophilic group (hereinafter referred to as "modified monomer (A)").

[0072] Examples of the hydrophilic group in the modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (in each formula, M represents H, a metal atom, or 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 are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. ) are examples of the hydrophilic group. Of these, -SO3M or -COOM is preferred. R 7 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the formula: The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (Group 1) or an alkaline earth metal (Group 2), with Na, K, or Li being preferred.

[0073] Examples of the "functional group capable of reacting by radical polymerization" in the modifying 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 is a group 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. The linking group for R can be represented by the formula: a Preferred linking groups include -CH=CH2 and -CF=CH 2、 -CH=CF 2、Examples include groups having an unsaturated bond such as -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, and -O-CF2-CF=CF2.

[0074] The modified monomer (A) has a functional group capable of reacting by radical polymerization, and therefore, when used in polymerization, it is presumed that it reacts with the fluorine-containing monomer at the initial stage of the polymerization reaction, forming highly stable particles having hydrophilic groups derived from the modified monomer (A). Therefore, it is considered that the number of particles increases when polymerization is carried out in the presence of the modified monomer (A).

[0075] The above-mentioned modifying monomer (A) may be used alone or in combination of two or more kinds.

[0076] As the modifying monomer (A), a compound having an unsaturated bond can be used.

[0077] The modifying monomer (A) is preferably at least one selected from the group consisting of compounds represented by the following formulas (4a) to (4e). CF2=CF-(CF2) n1 -Y 3 (4a) (wherein n1 represents an integer of 1 to 10, and Y 3 -SO3M 1 or -COOM 1 represents M 1 represents H, NH4 or an alkali metal. CF2=CF-(CF2C(CF3)F) n2 -Y 3 (4b) (wherein n2 represents an integer of 1 to 5, and Y 3 is the same as the definition above.) CF2=CF-O-(CFX 1 ) n3 -Y 3 (4c) (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, and Y 3 is the same as the definition above.) CF2=CF-O-(CF2CFX 1 O) n4 -CF2CF2-Y 3 (4d) (wherein n4 represents an integer of 1 to 10, and Y 3 and X 1 is the same as the definition above.) CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (4e) (In the formula, each 2 are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, and Y 3 is the same as the definition above.) The alkali metals include Na, K, and the like.

[0078] In the formula (4a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. 3 -COOM is advantageous in that it provides adequate water solubility and surface activity. 1 Preferably, M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0079] The perfluorovinyl alkyl compound represented by the above formula (4a) is, for example, CF2=CFCF2COOM 1 (In the formula, M 1 is the same as the definition above.

[0080] In the formula (4b), n2 is preferably an integer of 3 or less in terms of emulsifying ability, and Y 3-COOM is advantageous in that it provides adequate water solubility and surface activity. 1 Preferably, M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0081] In the formula (4c), n3 is preferably an integer of 5 or less in terms of water solubility, and Y 3 -COOM is advantageous in that it provides adequate water solubility and surface activity. 1 It is preferable that the above M 1 is preferably H or NH4 in terms of improving dispersion stability.

[0082] In the above formula (4d), the above X 1 is preferably -CF3 from the viewpoint of surface activity, n4 is preferably an integer of 5 or less from the viewpoint of water solubility, and Y 3 COOM has the advantage of providing moderate water solubility and surface activity. 1 It is preferable that the above M 1 is preferably H or NH4.

[0083] Examples of the perfluorovinyl ether compound represented by the above formula (4d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM 1 (In the formula, M 1 represents H, NH4 or an alkali metal.

[0084] In the formula (4e), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in terms of emulsifying ability. 3 COOM has the advantage of providing moderate water solubility and surface activity. 1 It is preferable that the above M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0085] Examples of the perfluorovinyl alkyl compound represented by the formula (4e) include CH2=CFCF2OCF(CF3)COOM 1 , CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM1(wherein, M 1 is the same as the definition above.

[0086] As the modifying monomer, in terms of improving the stretchability, binding strength, and flexibility of the composite sheet, at least one selected from the group consisting of HFP, PAVE, PFAE, and monomers having a polar group is preferred, at least one selected from the group consisting of HFP, perfluoro(methyl vinyl ether) [PMVE], perfluoro(propyl vinyl ether) [PPVE], PFBE, non-fluorinated monomers having acid anhydride residues, and modifying monomer (A) is more preferred, at least one selected from the group consisting of HFP, PMVE, PPVE, cyclic non-fluorinated monomers having acid anhydride residues, and compounds represented by general formula (4e) is even more preferred, at least one selected from the group consisting of HFP and PPVE is even more preferred, and HFP is even more preferred.

[0087] The TFE polymer may have a core-shell structure. Examples of TFE polymers having a core-shell structure include modified PTFE particles containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE. Examples of such modified PTFE include the PTFE described in JP-A-2005-527652.

[0088] The TFE-based polymer is preferably non-melt processable.

[0089] The content of the TFE polymer in the TFE 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, even 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, relative to the TFE polymer composition.

[0090] The TFE-based polymer composition of the present disclosure may contain a fluorine-containing compound having a hydrophilic group.

[0091] The hydrophilic group is, for example, -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a , -OCOM a , and -OM a (In the formula, M a -H, metal atom, -NR 1 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 1 is H or an organic group. The hydrophilic group may be an ionic group, and is preferably an anionic group.

[0092] Examples of the fluorine-containing compound having a hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less, i.e., a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 g / mol or less. The molecular weight of the fluorine-containing compound is preferably 800 or less, and more preferably 500 or less. Polymer particles obtained by polymerization in the presence of a fluorine-containing surfactant usually contain a fluorine-containing surfactant in addition to the TFE polymer. In this specification, the fluorine-containing surfactant is one that is used during polymerization. The fluorine-containing compound having a molecular weight of 1,000 or less may be a compound that is not added during polymerization, for example, a compound that is produced as a by-product during polymerization. When the fluorine-containing compound having a molecular weight of 1000 or less contains an anionic moiety and a cationic moiety, the fluorine-containing compound has a molecular weight of 1000 or less in the anionic moiety. The fluorine-containing compound having a molecular weight of 1000 or less does not include TFE polymers.

[0093] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include surfactants (anionic fluorine-containing surfactants) whose anionic moiety contains fluorine and whose molecular weight is 1000 or less. The "anionic moiety" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF2) n1 In the case of COOM, "F(CF2) n1 The "COO" part.

[0094] The anionic fluorine-containing surfactants include those represented by the 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 atoms have been substituted with F, and the alkylene group may contain one or more ether bonds, and some of the H atoms may have been substituted with Cl. Y 0 is an anionic group.

[0095] Y 0 The anionic group may be -COOM, -SO2M, or -SO3M, where M is H, a metal atom, NR 7 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 7is H or an organic group. The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li. 7 As for H or C 1-10 and may be an organic group of H or C 1-4 and may be an organic group of H or C 1-4 M may be an alkyl group of the formula: H, a metal atom, or NR 7 4, and 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. n0 may be one in which 50% or more of H is substituted with fluorine.

[0096] General formula (N 0 The compound represented by the general formula (N 1 ): X n0 -(CF2) m1 -Y 0 (N 1 ) (In the formula, X n0 is H, Cl, and F, m1 is an integer from 3 to 15, and Y 0 is as defined above, a compound represented by the general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 ) (In the formula, Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, and X n1 is F or CF3, and Y 0 is 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 having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, and Rf n3 is a linear or branched perfluoroalkylene group having 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 having 1 to 12 carbon atoms, which may contain an ether bond and / or a chlorine atom, and 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 ): [ka] (In the formula, X n2 , X n3 and X n4 Rf may be the same or different and are H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether bond. n5 is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms, which may contain an ether bond; L is a linking group; Y 0 is as defined above, where X n2 , X n3 , X n4 and Rf n5 The total number of carbon atoms is 18 or less.

[0097] General formula (N 0) More specifically, the compounds represented by the general formula (I) include perfluorocarboxylic acids (I), ω-H perfluorocarboxylic acids (II), general formula (III), perfluoroethercarboxylic acids (III), general formula (IV), perfluoroalkyl alkylene carboxylic acids (IV), general formula (V), perfluoroalkoxy fluorocarboxylic acids (V), general formula (VI), perfluoroalkyl sulfonic acids (VI), general formula (VII), ω-H perfluoro sulfonic acids (VII), general formula (VIII), perfluoroalkyl alkylene sulfonic acids (VIII), general formula (IX), alkyl alkylene carboxylic acids (IX), general formula (X), fluorocarboxylic acids (X), general formula (XI), alkoxy fluoro sulfonic acids (XI), general formula (XII), and general formula (XIII).

[0098] The perfluorocarboxylic acid (I) is represented by the general formula (I): F(CF2) n1 COOM (I) (wherein n1 is an integer of 3 to 14, and M is H, a metal atom, or NR 7 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 7 is H or an organic group.

[0099] The ω-H perfluorocarboxylic acid (II) is represented by the general formula (II): H(CF2) n2 COOM (II) (wherein n2 is an integer of 4 to 15, and M is as defined above).

[0100] The perfluoroethercarboxylic acid (III) is represented by the general formula (III): Rf 1 -O-(CF(CF3)CF2O) n3CF(CF3)COOM (III) (In the formula, 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.

[0101] The perfluoroalkyl alkylene carboxylic acid (IV) is represented by the general formula (IV): Rf 2 (CH2) n4 Rf 3 COOM (IV) (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, and 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.

[0102] The alkoxyfluorocarboxylic acid (V) is represented by the general formula (V): Rf 4 -O-CY 1 Y 2 CF2-COOM (V) (In the formula, Rf 4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain an ether bond and / or a chlorine atom, and Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.

[0103] The perfluoroalkylsulfonic acid (VI) is represented by the general formula (VI): F(CF2) n5 SO3M (VI) (wherein n5 is an integer of 3 to 14, and M is as defined above).

[0104] The ω-H perfluorosulfonic acid (VII) is represented by the general formula (VII): H(CF2) n6SO3M (VII) (wherein n6 is an integer of 4 to 14, and M is as defined above).

[0105] The perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the general formula (VIII): Rf 5 (CH2) n7 SO3M (VIII) (In the formula, 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.

[0106] The alkyl alkylene carboxylic acid (IX) is represented by the general formula (IX): Rf 6 (CH2) n8 COOM (IX) (In the formula, Rf 6 is a linear or branched partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer of 1 to 3, and M is as defined above.

[0107] The fluorocarboxylic acid (X) is represented by the general formula (X): Rf 7 -O-Rf 8 -O-CF2-COOM (X) (In the formula, Rf 7 is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether bond and / or a chlorine atom, and Rf 8 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above.

[0108] The alkoxyfluorosulfonic acid (XI) is represented by the general formula (XI): Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI) (In the formula, Rf 9 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, and which is partially or completely fluorinated; Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.

[0109] The compound (XII) is represented by the general formula (XII): [ka] (In the formula, X 1 , X 2 and X 3 Rf may be the same or different and are H, F, and linear or branched partially or fully fluorinated alkyl groups having 1 to 6 carbon atoms, which may contain ether bonds; 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 is an anionic group. 0 may be -COOM, -SO2M, or -SO3M, and may be -SO3M or COOM (wherein M is as defined above). Examples of L include a single bond, and a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms which may contain an ether bond.

[0110] The compound (XIII) is represented by the following general formula (XIII): Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM (XIII) (In the formula, Rf 11 is a fluoroalkyl group containing chlorine and having 1 to 5 carbon atoms, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above. Compound (XIII) is represented by the formula: CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10CF2COONH4 (a mixture having an average molecular weight of 750, wherein n9 and n10 are defined above).

[0111] Thus, examples of the anionic fluorine-containing surfactant include carboxylic acid surfactants and sulfonic acid surfactants.

[0112] The fluorine-containing surfactant may be one type of fluorine-containing surfactant or a mixture containing two or more types of fluorine-containing surfactants.

[0113] Examples of the fluorine-containing surfactant include compounds represented by the following formula: 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 [ka] (In each formula, M is H, metal atom, NR 74. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 7 is H or an organic group.

[0114] In each of the above formulas, M is H, a metal atom, or NR 7 4, and may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 7 4, which may be H, Na, K, Li, or NH4. R 7 is H or C 1-10 may be an organic group of H or C 1-4 may be an organic group of H or C 1-4 The alkyl group may be:

[0115] The content of the anionic fluorine-containing surfactant is preferably 25 mass ppb or less, more preferably 20 mass ppb or less, even more preferably 15 mass ppb or less, even more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, even more preferably 1 mass ppb or less, even more preferably less than 1 mass ppb, and particularly preferably less than the lower limit of quantitation, relative to the TFE-based polymer composition. The lower limit is not particularly limited, and may be an amount less than the lower limit of quantitation.

[0116] The amount of the anionic fluorine-containing surfactant is measured by the following method. Weigh out 1 g of sample, add 10 g (12.6 ml) of methanol, and ultrasonicate for 60 minutes to obtain an extract. The resulting extract is concentrated using an appropriate nitrogen purge, and the fluorine-containing compounds in the concentrated extract are measured by LC / MS / MS. Molecular weight information is extracted from the obtained LC / MS spectrum, and a match with the structural formula of the candidate fluorine-containing compound is confirmed. Aqueous solutions with five or more levels of standard substance content are prepared, and LC / MS analysis is performed on each solution. The relationship between content and area relative to that content is plotted, and a calibration curve is drawn. Using the above calibration curve, the area of ​​the LC / MS chromatogram of the fluorine-containing compounds in the extract is converted to the content of the fluorine-containing compounds. The lower limit of quantification in this measurement method is 10 ppb by mass.

[0117] The TFE polymer composition containing an anionic fluorine-containing surfactant can be obtained, for example, by polymerization using an anionic fluorine-containing surfactant.

[0118] The above-mentioned fluorine-containing compound having a hydrophilic group and a molecular weight of 1000 or less also includes a compound 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 (wherein m is 4 to 20. M 1 is H, 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), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. M 1 As the group, H is preferred.

[0119] M 1 Examples of the metal atom as the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specific examples include Na, K, and Li. The Four Rs5 may be the same or different. 5 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.

[0120] In general formula (1), m is preferably 6 or more, more preferably 8 or more, even more preferably 11 or more, even more preferably 13 or more, particularly preferably 15 or more, and is preferably 18 or less, more preferably 16 or less.

[0121] The TFE polymer composition of the present disclosure may contain one or more types of compound (1), but may also contain two or more types, or may also contain three or more types.

[0122] The content of compound (1) (the content of each component when two or more types are present) relative to the TFE-based polymer may be 10 ppm by mass or less, preferably 5,000 ppb by mass or less, more preferably 1,000 ppb by mass or less, even more preferably 500 ppb by mass or less, even more preferably 100 ppb by mass or less, even more preferably 50 ppb by mass or less, even more preferably 25 ppb by mass or less, and particularly preferably 10 ppb by mass or less. The lower limit is not particularly limited, but may be 0.1 mass ppb or 1 mass ppb.

[0123] The above-mentioned fluorine-containing compound having a hydrophilic group and a molecular weight of 1000 or less also includes 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 (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. M 2 As the group, H is preferred.

[0124] M 2 Examples of the metal atom as the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specific examples include Na, K, and Li. The Four Rs 5 may be the same or different. 5 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.

[0125] In general formula (2), n is preferably 6 or more, more preferably 8 or more, even more preferably 11 or more, even more preferably 13 or more, particularly preferably 15 or more, and is preferably 18 or less, more preferably 16 or less.

[0126] The TFE polymer composition of the present disclosure may contain one or more types of compound (2), but may also contain two or more types, or may also contain three or more types.

[0127] The content of compound (2) (content of each component when two or more types are present) may be 10 ppm by mass or less relative to the TFE-based polymer, preferably 5000 ppb by mass or less, more preferably 1000 ppb by mass or less, even more preferably 500 ppb by mass or less, even more preferably 100 ppb by mass or less, even more preferably 50 ppb by mass or less, even more preferably 25 ppb by mass or less, even more preferably 10 ppb by mass or less, even more preferably 1 ppb by mass or less, even more preferably less than 1 ppb by mass, and particularly preferably less than the lower limit of quantitation. The lower limit is not particularly limited, and may be an amount less than the lower limit of quantitation.

[0128] The TFE polymer composition containing the compound (1) and / or (2) can be obtained by using a hydrocarbon surfactant. The TFE polymer composition of the present disclosure may contain a hydrocarbon surfactant in addition to the TFE polymer and the compound (1) and / or (2). The content of the hydrocarbon surfactant in the TFE polymer composition is not particularly limited, but is usually 100 ppm by mass to 10% by mass. In the hydrocarbon surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0129] The TFE 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, metal atom, NR 5 4(R 5 may be the same or different and are H, 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.

[0130] "Substantially free of compound (3)" means that the content of compound (3) is 25 mass ppb or less relative to the TFE-based polymer. The content of compound (3) is preferably 20 mass ppb or less, more preferably 15 mass ppb or less, and even more preferably 10 mass ppb or less relative to the TFE-based polymer. The lower limit is not particularly limited, but may be 0 mass ppb, 0.1 mass ppb, or 1 mass ppb.

[0131] The contents of compounds (1), (2) and (3) are values ​​measured by liquid chromatography mass spectrometry as described in the Examples below.

[0132] The fluorine-containing compound having a hydrophilic group also includes a fluorine-containing compound having a hydrophilic group with a molecular weight of more than 1000, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight of more than 1000 g / mol.

[0133] Examples of the fluorine-containing compound having a hydrophilic group and a molecular weight of more than 1000 include polymer compounds having an ionic group. The TFE polymer is not included in the polymer compound.

[0134] The ionic group is preferably an anionic group, for example, a sulfate group, -COOM a (carboxylate group), phosphate group, -PO3M a (phosphonate group), -SO3M a (sulfonate group), -SO2M a (sulfinate group), -C(CF3)2OM a (In each formula, M a -H, metal atom, -NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group. Among them, -SO3M a , -SO2M a , -PO3M a and -COOM a At least one selected from the group consisting of -COOM is preferred. a is more preferred.

[0135] The content of the ionic group in the polymer compound is preferably 0.80 meq / g or more, more preferably 1.20 meq / g or more, even 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. The content may also be 10.0 meq / g or less, 8.00 meq / g or less, or 5.00 meq / g or less. The content of the ionic group can be calculated from the composition of the polymer compound.

[0136] The polymer compound preferably contains fluorine atoms, and the proportion of hydrogen atoms bonded to carbon atoms in the polymer compound that are substituted with fluorine atoms is preferably 50% or more. The "proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms" is calculated as the proportion 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 proportion of hydrogen atoms bonded to carbon atoms in the polymer compound that are substituted with fluorine atoms is not particularly limited, but is more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more, particularly preferably 95% or more, and most preferably 100%.

[0137] The polymeric compound preferably has an ion exchange ratio (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the polymeric backbone relative to the ionic group. Precursor groups that become ionic upon hydrolysis (e.g., -SO2F) are not considered ionic groups for purposes of determining the IXR. The IXR is preferably 0.5 or more, more preferably 1 or more, even more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. The IXR is preferably 43 or less, more preferably 33 or less, and even more preferably 23 or less. In the polymeric compounds, the ionic groups are typically distributed along the polymer backbone, and the polymeric compounds preferably comprise recurring side chains attached to the polymer backbone, the side chains carrying the ionic groups.

[0138] The polymer compound is preferably a water-soluble polymer compound. "Water-soluble" refers to the property of being easily dissolved or dispersed in an aqueous medium. For example, the particle size of a water-soluble polymer compound cannot be measured by dynamic light scattering (DLS), or the particle size is 5 nm or less. On the other hand, for example, the particle size of a water-insoluble polymer compound can be measured by dynamic light scattering (DLS) to be greater than 5 nm.

[0139] The number average molecular weight of the polymer compound is 0.1 × 10 4 More than 0.15 x 10 is preferred 4 More preferably, 0.2 × 10 4 More preferably, 0.3 × 10 4 More preferably, 0.5×10 4 More preferably, 1.0×10 4 More preferably, 2.0 × 10 4 More than 3.0 × 10 is particularly preferable. 4 More than 75.0×10 4 The following is preferable: 50.0 x 10 4 Less than 40.0 x 10 is more preferable. 4 More preferably, 30.0 x 10 4 The following is particularly preferred: 20.0 × 10 4 The following are particularly preferred:

[0140] The weight average molecular weight of the polymer compound is 0.1 × 10 4 More than 0.2 x 10 is preferred. 4 More preferably, 0.4 × 10 4 More preferably, 0.6×10 4 More preferably, 1.0×10 4 More preferably, 2.0×10 4More than 5.0 × 10 is particularly preferable. 4 More than 150.0×10 4 The following is preferable: 100.0 x 10 4 Less than 80.0 x 10 is preferable. 4 More preferably, 60.0 x 10 4 The following is particularly preferred: 40.0 × 10 4 The following are particularly preferred:

[0141] The 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. When GPC measurement is not possible, the number-average molecular weight of the polymer compound 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.

[0142] The polymer compound preferably contains substantially no fractions having a molecular weight of 1,000 or less, more preferably contains substantially no fractions having a molecular weight of less than 1,500, even more preferably contains substantially no fractions having a molecular weight of less than 2,000, and particularly preferably contains substantially no fractions having a molecular weight of less than 3,000. "Substantially free of the fraction" means that the content of the fraction relative to the polymer compound is 3.0% by mass or less, 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. The content of the above fractions can be measured by gel permeation chromatography (GPC) or liquid chromatography-mass spectrometry (LC-MS).

[0143] The polymer compound is preferably substantially free of fluorine-containing compounds having a molecular weight of not more than 1000. "Substantially free of fluorine-containing compounds" means that the amount of the fluorine-containing compounds is not more than 25 ppb by mass relative to the polymer compound. The amount of the fluorine-containing compound is more preferably less than 25 mass ppb, even more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, even more preferably 5 mass ppb or less, even more preferably 3 mass ppb or less, even 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 below the detection limit. The above-mentioned fluorine-containing compound having a molecular weight of 1,000 or less and a method for quantifying it will be described later.

[0144] The polymer compound is preferably at least one selected from the group consisting of a polymer (I) containing a polymer 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 CF; 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; and m is an integer of 1 or more. 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 each independently represents a C optionally substituted by one or more fluorine atoms; 1-6 is an alkylene group, p's are each independently 0 or 1; Each q is independently 0 or 1; X A are each independently a single bond or a divalent to decavalent group, T X and T X (i) each independently represents a C1-C alkyl group which may contain one or more of H, O, and Cl and does not have the anionic group; 24 (hydro)(fluoro)carbon groups, and (ii) a C1-C group containing at least one of the anionic groups. 24 (hydro)(fluoro)carbon groups.)

[0145] The polymer (I) is a polymer containing polymerized units (I) based on the monomer (I). The 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) (In the formula, X 1 and X 3are each independently F, Cl, H, or CF; X 2 is H, F, an alkyl group or a fluorine-containing 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 fluorine-containing alkyl group; and m is an integer of 1 or more. X 2 is preferably F, Cl, H or CF3. 1 and Z 2 is preferably F or CF3.

[0146] In the present disclosure, the anionic group includes functional groups that provide anionic groups such as sulfate groups, carboxylate groups, acid groups such as -COOH, acid salt groups such as -COONH4, etc. Examples of anionic groups include sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, sulfinate groups, or -C(CF3)2OM. a (In the formula, M a -H, metal atom, -NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group.

[0147] In the present disclosure, one or more types of monomers can be used as the monomer (I) represented by general formula (I).

[0148] R is a linking group. In the present disclosure, a "linking group" is an (m+1)-valent linking group, and when m is 1, it is a divalent linking group. The linking group may be a single bond and 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. There is no upper limit, but it may be, for example, 100 or less, or 50 or less.

[0149] The linking group may be linear or branched, cyclic or acyclic in structure, 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 carbon atoms but may be a catenary heteroatom such as oxygen, sulfur, or nitrogen.

[0150] m is an integer of 1 or more, preferably 1 or 2, and 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 structure when m is 1 in general formula (I) will be described.

[0151] R is preferably a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0152] It is also preferred that the polymer (I) is highly fluorinated, e.g., containing phosphate moieties (e.g., CH2OP(O)(OM a ) 2) and sulfate group moieties (e.g., CH2OS(O)2OM a ) such as anionic groups (A 0 ), it is preferred that 80% or more, 90% or more, 95% or more, or 100% of the C—H bonds in the polymer (I) are substituted with C—F bonds.

[0153] The monomer (I) and the polymer (I) contain an anionic group (A 0 ) except for the C—F bond, it is also preferable that the compound has no C—H bond. 1 , X 2 , and X 3are all F, and R is preferably a perfluoroalkylene group having one or more carbon atoms, and the perfluoroalkylene group may be either linear or branched, may be 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.

[0154] The monomer (I) and the polymer (I) may be partially fluorinated. That is, the monomer (I) and the polymer (I) may contain an anionic group (A 0 ), it is also preferred that the alkyl group has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0155] 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 preferred, -COOM a , -SO3M a, -OSO3M a or C(CF3)2OM a is more preferred, -SO3M a , -COOM a or P(O)(OM a )2 is more preferred, and -SO3M a or COOM a is particularly preferred, and -COOM a is most preferred.

[0156] M a is H, metal atom, NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group.

[0157] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0158] M a The group may be -H, a metal atom, or NR 2 4 is preferred, and -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 2 4 is more preferred, -H, -Na, -K, -Li or NH4 is even more preferred, -H, -Na, -K or NH4 is even more preferred, -H, -Na or NH4 is especially preferred, and -H or NH4 is most preferred.

[0159] In the polymer (I), each polymer unit (I) may have a different anionic group or may have the same anionic group.

[0160] The monomer (I) is also preferably a monomer represented by the general formula (Ia). The polymer (I) is also preferably a polymer containing polymerized units (Ia) based on a monomer represented by general formula (Ia). CF2=CF-O-Rf 0 -A 0 (Ia) (In the formula, A 0is an anionic group, and Rf 0 is a perfluorinated divalent linking group which may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and which optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0161] The monomer (I) is also preferably a monomer represented by the general formula (Ib). The polymer (I) is also preferably a polymer containing polymerized units (Ib) based on a monomer represented by general formula (Ib). CH2=CH-O-Rf 0 -A 0 (Ib) (In the formula, A 0 is an anionic group, and Rf 0 is a perfluorinated divalent linking group defined by formula Ia.

[0162] In general formula (I), A 0 is a sulfate group. 0 For example, -CH2OSO3M a , -CH2CH2OSO3M a , or -SO2NR'CH2CH2OSO3M a wherein R' is H or an alkyl group having 1 to 4 carbon atoms; M a is the same as above.

[0163] A 0 is a sulfate group, examples of the monomer represented by 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 ), CH2=CH(O(CF2)4CH2OSO3M a), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M a ), CH2=CH(OCF2CF2CH2OSO3M a ), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M a ), CH2=CH(OCF2CF2CF2CH2OSO3M a In the above formula, M a is the same as above.

[0164] In general formula (I), A 0 In one preferred embodiment, A is a sulfonate group. 0 For example, -SO3M a where M a is the same as above.

[0165] A 0 is a sulfonate group, the monomer represented by general formula (I) is 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 In the above formula, M a is the same as above.

[0166] In general formula (I), A 0 In one preferred embodiment, A is a sulfinate group. 0 For example, -SO2M a where M a is the same as above.

[0167] A 0 is a sulfinate group, the monomer represented by general formula (I) is 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 In the above formula, M a is the same as above.

[0168] In general formula (I), A 0 A is preferably a carboxylate group. 0 For example, COOM a or SO2NR'CH2COOM a wherein R' is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above. A 0 is a carboxylate group, the monomer represented by general formula (I) is 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 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.

[0169] In general formula (I), A 0 In one preferred embodiment, A is a phosphate group. 0 Examples of the alkoxy group include -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, wherein R' is an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0170] A 0 is a phosphate, the monomer represented by general formula (I) may be 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) and the like. a is the same as above.

[0171] In general formula (I), A 0 In one preferred embodiment, A is a phosphonate group. 0 is a phosphonate group, the monomer represented by general formula (I) may be 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 which M a is the same as above.

[0172] The monomer (I) is preferably a monomer (1) represented by the general formula (1). The polymer (I) is preferably a polymer (1) containing polymerized units (1) based on a monomer represented by general formula (1). CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X's may be the same or different and each represent -H or F; Y's may be -H, -F, an alkyl group or a fluorine-containing alkyl group; Z's may be the same or different and each represent -H, -F, an alkyl group or a fluoroalkyl group; Rf's may be a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond; A's may be -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a -H, metal atom, -NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group.) However, at least one of X, Y, and Z contains a fluorine atom.)

[0173] In the production method of the present disclosure, the monomer (1) represented by general formula (1) may be copolymerized with other monomers. The polymer (1) may be a homopolymer of the monomer (1) represented by the general formula (1), or may be a copolymer with other monomers.

[0174] The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0175] In general formula (1), X is -H or F. Both Xs may be -F, or at least one X may be -H. For example, one X may be -F and the other may be -H, or both Xs may be -H.

[0176] In general formula (1), 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 one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. Y is preferably -H, -F or CF3, and more preferably -F.

[0177] In general formula (1), Z's are the same or different and represent -H, -F, an alkyl group, or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. Z's are preferably -H, -F, or CF3, and more preferably -F.

[0178] 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.

[0179] In the general formula (1), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond.

[0180] The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. The number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CF2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0181] The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorine-containing alkylene group having an ether bond is, for example, a group represented by the general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F; Z respectively 4 is also preferably a divalent group represented by the formula: H, F, or CF3; p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5).

[0182] Specific examples of the fluorine-containing alkylene group having an ether bond include -CF2CF(CF3)OCF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)- (wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) nExamples include -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0183] In the general formula (1), A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a is H, metal atom, NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group).

[0184] R 2 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the formula:

[0185] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0186] M a The group may be H, a metal atom, or NR 2 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 2 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, H, Na, K or NH4 is even more preferred, H, Na or NH4 is particularly preferred, and H or NH4 is most preferred.

[0187] As for A, -COOM a or SO3M a is preferred, -COOM a is more preferred.

[0188] Examples of the monomer represented by general formula (1) include a monomer represented by general formula (1a): CX2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-A (1a) (wherein each X is the same and represents F or H, n5 represents 0 or an integer of 1 to 10, and A is as defined above) is an example.

[0189] In general formula (1a), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in that particles with a small primary particle size can be obtained.

[0190] In the production method of the present disclosure, the monomer represented by general formula (1a) may be copolymerized with other monomers. The polymer (1) may be a homopolymer of the monomer represented by the general formula (1a) or a copolymer with other monomers.

[0191] The monomer (1) is preferably a monomer represented by the general formula (1A). The polymerized unit (1) is preferably a polymerized unit (1A) based on a monomer represented by general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (wherein Rf and A are the same as above.)

[0192] In the production method of the present disclosure, the monomer represented by general formula (1A) may be copolymerized with other monomers. The polymer (1) may be a homopolymer of the monomer represented by the general formula (1A) or a copolymer with other monomers.

[0193] Specific examples of the monomer represented by formula (1A) include the monomer represented by the general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F; Z respectively 4 is H, F, or CF3; p1+q1+r1 is an integer of 0 to 10; s1 is 0 or 1; t1 is an integer of 0 to 5, provided that Z 3 and Z 4 are both H, then p1+q1+r1+s1 is not 0; A is the same as defined above). More specifically, [ka] Among them, [ka] It is preferable that:

[0194] The monomer represented by the general formula (1A) is a monomer represented by the general formula (1A) in which A is -COOM a is preferred, and in particular CH2=CFCF2OCF(CF3)COOM a , and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM a (In the formula, M a is as defined above.) and CH2=CFCF2OCF(CF3)COOM a is more preferred.

[0195] Further, examples of the monomer represented by the general formula (1) include the monomer represented by the following formula: CF2=CFCF2-O-Rf-A (wherein Rf and A are the same as above)

[0196] More specifically, [ka] etc.

[0197] The monomer (I) is also preferably a monomer (2) represented by the general formula (2). The polymer (I) is also preferably a polymer (2) containing polymerized units (2) based on a monomer represented by general formula (2). CX2=CY(-O-Rf-A) (2) (In the formula, X's are the same or different and represent -H or F; Y represents -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf represents a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond or a keto group; and A is the same as defined above.)

[0198] In the production method of the present disclosure, the monomer (2) represented by general formula (2) may be copolymerized with other monomers. The polymer (2) may be a homopolymer of the monomer represented by the general formula (2) or a copolymer with other monomers.

[0199] In general formula (2), X is -H or F. Both Xs may be -F, or at least one X may be -H. For example, one X may be -F and the other may be -H, or both Xs may be -H.

[0200] In 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 one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. Y is preferably -H, -F, or CF3, and more preferably -F.

[0201] In 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.

[0202] In general formula (2), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, or a fluorine-containing alkylene group having a keto group having 2 to 100 carbon atoms. The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and contains an ether bond between carbon atoms.

[0203] The number of carbon atoms in the fluorine-containing alkylene group of Rf is preferably 2 or more. Also, it is preferably 30 or less, more preferably 20 or less, even 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-, and the like. The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0204] The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less. The fluorine-containing alkylene group having an ether bond is, for example, a group represented by the general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F; Z respectively 4 is also preferably a divalent group represented by the formula: H, F, or CF3; p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5).

[0205] Specific examples of the fluorine-containing alkylene group having an ether bond include -CFCF(CF)OCFCF-, -CFCF(CF)OCFCFCFCF-, -CF(CF)CF-O-CF(CF)-, -(CF(CF)CF-O) n -CF(CF3)- (wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0206] The carbon number of the fluorine-containing alkylene group having a keto group is preferably 3 or more. The carbon number of the fluorine-containing alkylene group having a keto group is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less.

[0207] Specific examples of the fluorine-containing alkylene group having a keto group include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, etc. The fluorine-containing alkylene group having a keto group is preferably a perfluoroalkylene group.

[0208] 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 in which water is added to the keto group include -CFCF(CF)C(OH)-CF-, -CFCF(CF)C(OH)-CFCF-, -CFCF(CF)C(OH)-CFCFCF-, and -CFCF(CF)C(OH)-CFCFCFCF-.

[0209] The monomer represented by general formula (2) is preferably at least one selected from the group consisting of monomers represented by general formulas (2a), (2b), (2c), (2d), (2e), (2f) and (2g). CF2=CF-O-(CF2) n1 -A (2a) (wherein 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) (wherein n2 represents an integer of 1 to 5, and A is 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 as defined above. CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -A (2d) (wherein n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and A and X 1 is the same as the definition above.) CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-A (2e) (wherein n5 represents an integer of 0 to 10, and A and X 1 is the same as the definition above.) CF2=CF-O-(CF2) n7 -O-(CF2) n8 -A (2f) (In the formula, n7 represents an integer of 1 to 10, n8 represents an integer of 1 to 3, and A is as defined above.) CF2=CF[OCF2CF(CF3)] n9 O(CF2) n10 O[CF(CF3)CF2O] n11 CF(CF3)-A (2g) (In the formula, n9 represents an integer of 0 to 5, n10 represents an integer of 1 to 8, and n11 represents an integer of 0 to 5. A is as defined above.)

[0210] In the general formula (2a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.

[0211] 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 definition above.

[0212] In general formula (2b), n2 is preferably an integer of 3 or less, from the viewpoint of the dispersion stability of the resulting composition.

[0213] In the general formula (2c), n3 is preferably an integer of 5 or less in terms of water solubility, and A is preferably -COOM a It is preferable that the above M a is preferably H, Na or NH4.

[0214] In general formula (2d), X 1 is preferably -CF3 from the viewpoint of dispersion stability of the composition, n4 is preferably an integer of 5 or less from the viewpoint of water solubility, and A is preferably -COOM aPreferably, M a is preferably H, Na or NH4.

[0215] Examples of the monomer represented by 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 (In the formula, M a represents H, NH4 or an alkali metal.

[0216] In the general formula (2e), n5 is preferably an integer of 5 or less in terms of water solubility, and A is preferably -COOM a Preferably, M a is preferably H or NH4.

[0217] Examples of the monomer represented by general formula (2e) include CF2=CFOCF2CF2CF2COOM a (In the formula, M a represents H, Na, NH4 or an alkali metal.

[0218] In the general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, and A is preferably -COOM a or SO3M a Preferably, -COOM a is more preferable. a is preferably H, Na, K or NH4.

[0219] Examples of the monomer represented by general formula (2f) include CF2=CF-O-(CF2)3-O-CF2-COOM a (In the formula, Ma represents H, NH4 or an alkali metal.

[0220] In the 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 Preferably, -COOM a is more preferable. a is preferably H, Na, K or NH4.

[0221] 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 (In the formula, M a represents H, NH4 or an alkali metal.

[0222] The monomer (I) is also preferably a monomer (3) represented by the general formula (3). The polymer (I) is also preferably a polymer (3) containing polymerized units (3) based on a monomer represented by general formula (3). CX2=CY(-Rf-A) (3) (In the formula, X's are the same or different and represent -H or F; Y represents -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf represents a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond; and A is the same as defined above.)

[0223] In the production method of the present disclosure, the monomer (3) represented by 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.

[0224] The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0225] In general formula (3), Rf is preferably a fluorine-containing alkylene group having a carbon number of 1 to 40. In general formula (3), at least one of X and Y preferably contains a fluorine atom.

[0226] The monomer represented by general formula (3) is represented by general formula (3a): CF2=CF-(CF2) n1 -A (3a) (wherein n1 represents an integer of 1 to 10, and A is as defined above), and a monomer represented by general formula (3b): CF2=CF-(CF2C(CF3)F) n2 -A (3b) (wherein n2 represents an integer of 1 to 5, and A is as defined above), is preferred.

[0227] In the general formula (3a) and the general formula (3b), A is -SO3M a or COOM a is preferred, and M a is H, metal atom, NR 2 4. It is preferably an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 2 represents H or an organic group.

[0228] In the general formula (3a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less.a Preferably, M a is preferably H or NH4.

[0229] Examples of the monomer represented by general formula (3a) include CF2=CFCF2COOM a (In the formula, M a is the same as the definition above.

[0230] In the general formula (3b), n2 is preferably an integer of 3 or less from the viewpoint of the dispersion stability of the resulting composition, and A is preferably -COOM a Preferably, M a is preferably H or NH4.

[0231] Next, a preferred configuration when m in general formula (I) is an integer of 2 or more will be described.

[0232] It is also preferable that the monomer (I) is at least one selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). It is also preferable that the polymer (I) is a polymer (4) containing polymerization units (4) based on at least one monomer selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). CF2=CF-CF2-OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4a) (In the formula, Z 1 , Z 2 and A are the same as 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-OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4b) (In the formula, Z1 , Z 2 , A, Q F1 and Q F2 is the same as above)

[0233] The monomers represented by general formula (4a) and general formula (4b) include: [ka] etc.

[0234] The monomer (I) is preferably at least one selected from the group consisting of the monomer (1), the monomer (2) and the monomer (3), more preferably the monomer (1), and further preferably the monomer (1A). The polymer (I) is preferably at least one selected from the group consisting of polymer (1), polymer (2) and polymer (3), and more preferably polymer (1).

[0235] In the present disclosure, the monomer (I) may be copolymerized with other monomers. The polymer (I) may be a homopolymer consisting of only the polymerized unit (I), or may be a copolymer containing the polymerized unit (I) and a polymerized unit based on another monomer copolymerizable with the monomer represented by general formula (I). From the viewpoint of solubility in an aqueous medium, a homopolymer consisting of only the polymerized unit (I) is preferred. The polymerized units (I) may be the same or different in each occurrence, and the polymer (I) may contain polymerized units (I) based on two or more different monomers represented by general formula (I).

[0236] The other monomer is preferably 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). Fluorine-containing ethylenic monomers having 2 or 3 carbon atoms are also preferred. Specific 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-form), and CHF=CHCF3 (Z-form). Among these, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl) and vinylidene fluoride (CH2=CF2) is preferred in terms of good copolymerizability, and at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride is more preferred. Therefore, the polymerized units based on the other monomer are preferably polymerized units based on tetrafluoroethylene. The polymerized units based on the other monomers may be the same or different in each occurrence, and the polymer (I) may contain polymerized units based on two or more different other monomers.

[0237] The other monomers also include those represented by the general formula (n1-2): [ka] (In the formula, X 1 , X 2 are the same or different H or F;X 3 is H, F, Cl, CH3 or CF3; X 4 , X 5 are the same or different and are H or F; a and c are the same or different and are 0 or 1. Rf 3 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond).

[0238] Specifically, 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)).

[0239] Examples of the other monomers include those of formula (n2-1): [ka] (In the formula, X 9 is H, F or CH3; Rf 4 Also included are fluorine-containing acrylate monomers represented by Rf (a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond). 4 The base is [ka] (wherein d3 is an integer of 1 to 4; e3 is an integer of 1 to 10), etc.

[0240] Examples of the other monomers include those of formula (n2-2): CH2=CHO-Rf 5 (n2-2) (In the formula, Rf 5 Also included are fluorine-containing vinyl ethers represented by the formula (wherein R is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond).

[0241] Specific examples of the monomer of general formula (n2-2) include: [ka] (wherein e6 is an integer of 1 to 10) are preferred.

[0242] More specifically, [ka] etc.

[0243] Others include those of general formula (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (In the formula, Rf 6 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond), a fluorine-containing allyl ether represented by the general formula (n2-4): CH2=CH-Rf 7 (n2-4) (In the formula, Rf7 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond), and the like.

[0244] Specific examples of the monomers represented by general formulas (n2-3) and (n2-4) include: [ka] and the like monomers.

[0245] The polymer (I) usually has a terminal group. The terminal group is a terminal group generated during polymerization, and typical terminal groups are independently selected from hydrogen, iodine, bromine, linear or branched alkyl groups, and linear or branched fluoroalkyl groups, and may optionally contain at least one catenary heteroatom. The alkyl group or fluoroalkyl group preferably has 1 to 20 carbon atoms. These terminal groups are generally generated from the initiator or chain transfer agent used to form the polymer (I) or during the chain transfer reaction.

[0246] In the polymer (I), the content of the polymerized units (I) relative to all polymerized units is, in order of preference, 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, and 90 mol% or more. The content of the polymerized units (I) is particularly preferably substantially 100 mol%, and the polymer (I) is most preferably composed only of the polymerized units (I).

[0247] In polymer (I), the content of polymerized units based on other monomers copolymerizable with the monomer represented by general formula (I) is, in order of preference, 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, and 10 mol% or less, based on all polymerized units. It is particularly preferred that the content of polymerized units based on other monomers copolymerizable with the monomer represented by general formula (I) is substantially 0 mol%, and it is most preferred that polymer (I) does not contain polymerized units based on other monomers.

[0248] The number average molecular weight of the polymer (I) is 0.1 × 10 4 More than 0.2 × 10 is preferable. 4 More preferably, 0.3 × 10 4 More preferably, 0.4×10 4 More preferably, 0.5×10 4 More than 1.0 × 10 4 More than 3.0 × 10 is particularly preferable. 4 The above is particularly preferable, and 3.1 × 10 4 More than 75.0×10 4 The following is preferable: 50.0 x 10 4 Less than 40.0 x 10 is more preferable. 4 More preferably, 30.0 x 10 4 The following is particularly preferred: 20.0 × 10 4 The following are particularly preferred. The number average molecular weight and 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 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.

[0249] The weight average molecular weight of the polymer (I) is preferably 0.2×10 4That's 0.4 x 10 4 That's 0.6 x 10 4 That's 0.8 x 10 4 That's it, 1.0 x 10 4 That's it, 2.0 x 10 4 That's it, 5.0 x 10 4 That's it, 10.0 x 10 4 That's it, 15.0 x 10 4 That's it, 20.0 x 10 4 That's it, 25.0 x 10 4 The weight average molecular weight of the polymer (I) is preferably 150.0×10 4 Below, 100.0 x 10 4 Below, 60.0 x 10 4 Below, 50.0 x 10 4 Below, 40.0 x 10 4 The following is the result.

[0250] The polymer (I) preferably has an ion exchange ratio (IXR) of 53 or less, where IXR is defined as the number of carbon atoms in the polymer backbone relative to the ionic group. Precursor groups that become ionic upon hydrolysis (e.g., -SOF) are not considered ionic groups for purposes of determining IXR.

[0251] IXR is preferably 0.5 or more, more preferably 1 or more, even more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. IXR is more preferably 43 or less, even more preferably 33 or less, and particularly preferably 23 or less.

[0252] The ion exchange capacity of the polymer (I) is, in order of preference, 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, and 3.50 meq / g or more. The ion exchange capacity is the content of ionic groups (anionic groups) in the polymer (I) and can be calculated from the composition of the polymer (I).

[0253] In polymer (I), the ionic (anionic) groups are typically distributed along the polymer backbone. The polymer (I) comprises a polymer backbone with recurring side chains attached to the backbone, which preferably carry ionic groups.

[0254] Preferably, polymer (I) comprises ionic groups having a pKa of less than 10, more preferably less than 7. The ionic groups of polymer (I) are preferably selected from the group consisting of sulfonate, carboxylate, phosphonate, and phosphate.

[0255] The terms "sulfonate, carboxylate, phosphonate, and phosphate" are intended to refer to the respective salts or the respective acids capable of forming salts. When salts are used, preferably the salts are alkali metal salts or ammonium salts. A preferred ionic group is a sulfonate group.

[0256] The polymer (I) is preferably water-soluble. Water-soluble means the property of being easily dissolved or dispersed in an aqueous medium. The particle size of the water-soluble polymer (I) cannot be measured by dynamic light scattering (DLS), for example, or the particle size is 5 nm or less.

[0257] The viscosity of an aqueous solution of polymer (I) is preferably 5.0 mPa s or more, more preferably 8.0 mPa s or more, even more preferably 10.0 mPa s or more, particularly preferably 12.0 mPa s or more, and most preferably 14.0 mPa s or more, and preferably 100.0 mPa s or less, more preferably 50.0 mPa s or less, even more preferably 25.0 mPa s or less, and especially preferably 20.0 mPa s or less.

[0258] The viscosity of an aqueous solution of polymer (I) can be determined by adjusting the content of polymer (I) in the aqueous solution to 33 mass % based on the amount of the aqueous solution, and measuring the viscosity of the resulting aqueous solution at 20°C using a tuning fork vibro viscometer (model number: SV-10) manufactured by A&D Corporation.

[0259] The critical micelle concentration (CMC) of the polymer (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less.

[0260] The critical micelle concentration of the polymer (I) can be determined by measuring the surface tension, for example, using a surface tensiometer CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.

[0261] The acid value of the polymer (I) is preferably 60 or more, more preferably 90 or more, even more preferably 120 or more, particularly preferably 150 or more, and most preferably 180 or more. The upper limit is not particularly limited, but is preferably 300 or less.

[0262] The acid value of the polymer (I) is determined by the presence of an anionic group other than the acid functional group, such as -COOM. a , -SO3M a , -OSO3M a or C(CF3)2OM a (M a is the metal atom, NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 If the compound has a hydroxyl group (H or an organic group), these groups can be converted to acid forms and then measured by acid-base titration.

[0263] Compound (II) is represented by 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 -Rf1 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 optionally substituted by one or more fluorine atoms; 1-6 is an alkylene group, p's are each independently 0 or 1; Each q is independently 0 or 1; X A are each independently a single bond or a divalent to decavalent group, T X and T X (i) each independently represents a C1-C alkyl group which may contain one or more of H, O, and Cl and does not have the anionic group; 24 (hydro)(fluoro)carbon groups, and (ii) a C1-C group containing at least one of the anionic groups. 24 (hydro)(fluoro)carbon groups.)

[0264] In formula (II), R FA1 is -Rf 1 p -R F -O q -It is.

[0265] In formula (II), R FA2 is -Rf 2 p -R FX -O q -It is.

[0266] In formula (II), Rf 1and Rf 2 each independently represents a C optionally substituted by one or more fluorine atoms; 1-6 It is an alkylene group.

[0267] C optionally substituted with one or more fluorine atoms 1-6 "C" in the alkylene group 1-6 The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0268] Rf 1 and Rf 2 is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0269] Above C 1-6 The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0270] In the above formula, each p is independently 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0271] In the above formula, each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0272] In formula (II), R F is a divalent fluoropolyether group.

[0273] R F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or greater.] It is a group represented by the following formula:

[0274] R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or greater.

[0275] a, b, c, d, e and f may each independently be an integer of preferably 0 to 100, more preferably an integer of 0 to 50.

[0276] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, even 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, even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0277] These repeating units may be linear or branched, and may contain a ring structure. For example, -(OCF 12 )- may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(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 -(OCFCFCF)-, -(OCF(CF)CF)-, and -(OCFCF(CF))-. -(OCF)- may be any of -(OCFCF)- and -(OCF(CF))-.

[0278] The ring structure may be a three-, four-, five-, or six-membered ring as shown below. [ka] [In the formula, * indicates the bonding position.]

[0279] The ring structure may be preferably a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0280] The repeating unit having a ring structure may preferably be the following unit. [ka] [In the formula, * indicates the bonding position.]

[0281] In one embodiment, the repeating unit is linear.

[0282] In one embodiment, the repeat unit is branched.

[0283] In one embodiment, R F is a group represented by any one of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 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 each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent 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 occurrence of each repeating unit enclosed in parentheses with c, d, e, or f is arbitrary in the formula. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 are 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. -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are 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’ are 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 teeth, [ka] (In the formula, * indicates the bonding position.) ]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 )a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0284] 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, an integer of 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), 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)), more preferably (OCF2CF2).

[0285] In the formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. 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 formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) is a group represented by -(OC2F4) e -(OCF2) f It may also be a group represented by the formula -.

[0286] In the above formula (f3), R 6is 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 thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples include 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -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 12 may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or-(OC2F4-OC4F8) g -It is.

[0287] In the above formula (f4), R 6 , R 7 and g have the same meanings as those in the formula (f3) above, and have the same embodiments. 6’ , R 7’ and g' are R 6 , R 7 and g have the same meaning and similar aspects. r is preferably [ka] [In the formula, * indicates the bonding position.] and more preferably [ka] [In the formula, * indicates the bonding position.] is.

[0288] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 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.

[0289] 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.

[0290] In one embodiment, R F is a group represented by the above formula (f1).

[0291] In one embodiment, R F is a group represented by the above formula (f2).

[0292] In one embodiment, R F is a group represented by the above formula (f3) or (f4).

[0293] In one embodiment, R F is a group represented by the above formula (f3).

[0294] In one embodiment, R F is a group represented by the above formula (f4).

[0295] In one embodiment, R F is a group represented by the above formula (f5).

[0296] In one embodiment, R F is a group represented by the above formula (f6).

[0297] R F In the formula, the ratio of e to f (hereinafter referred to as "e / f ratio") is preferably 0.1 to 10, more preferably 0.2 to 5, even more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85. By making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the more the stability of the compound can be improved.

[0298] In one embodiment, from the viewpoint of heat resistance, the e / f ratio may be preferably 1.0 or more, and more preferably 1.0 to 2.0.

[0299] In formula (II), R FX is a divalent fluoropolyether group containing an anionic group. The anionic group includes functional groups that provide anionic groups such as sulfate groups, carboxylate groups, acid groups such as -COOH, acid-base groups such as -COONH4, etc. Examples of anionic groups include sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, and -C(CF3)2OM. a (In the formula, M a -H, metal atom, -NR 2 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 2 is H or an organic group.

[0300] R FX The fluoropolyether group in the formula (I) may be a group in which one or more hydrogen atoms of a polyether group have been substituted with fluorine atoms, and is preferably a perfluoropolyether group.

[0301] R FX is a repeating unit, (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); [where: G x is a C1-C5 perfluoro(oxy)alkylene group containing at least one anionic group as detailed above. It is preferably a divalent fluoropolyether group having a unit selected from the group consisting of:

[0302] In addition, R F and R FX The repeating units constituting the formula (I) may be present in any order.

[0303] In the above compound (II), R FA1 and R FA2 The number average molecular weight of the R moiety is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. FA1 and R FA2 The number average molecular weight of 19 The value is measured by F-NMR.

[0304] In formula (II), X A is the fluoropolyether part (R FA1 and R FA2 ) and a moiety containing an anionic group (T X and T X Therefore, the X A may be a single bond or any other group as long as the compound represented by formula (II) can exist stably.

[0305] X Aare each independently a single bond or a divalent to decavalent group.

[0306] X A are each independently preferably a single bond or a divalent to decavalent organic group.

[0307] In one embodiment, X A does not contain a siloxane bond (-Si-O-Si-).

[0308] Above X A The divalent to decavalent group in the formula (I) is preferably a divalent to octavalent group. In one embodiment, the divalent to decavalent group is preferably a divalent to tetravalent group, and more preferably a divalent group. In another embodiment, the divalent to decavalent group is preferably a trivalent to octavalent group, and more preferably a trivalent to hexavalent group.

[0309] In one embodiment, X A is a single bond or a divalent group.

[0310] 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, and even more preferably a divalent organic group.

[0311] In one embodiment, X A is a trivalent to hexavalent group, preferably a trivalent to hexavalent organic group.

[0312] In one embodiment, X A is a trivalent group, preferably a trivalent organic group.

[0313] In one embodiment, X A is a single bond.

[0314] In another embodiment, X A is a divalent organic group.

[0315] In one embodiment, X A Examples of the group include a single bond and the group represented by the following formula: -(R 51) p5 -(X 51 ) q5 - [In formula: R 51 is a single bond, -(CH2) s5 - or an o-, m- or p-phenylene group, preferably -(CH2) s5 - and s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; X 51 is -(X 52 ) l5 - represents X 52 are each independently -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 -, -NR 54 - and -(CH2) n5 represents a group selected from the group consisting of - R 53 are each independently a phenyl group, C 1-6 Alkyl group or C 1-6 represents an alkoxy group, preferably a phenyl group or C 1-6 is an alkyl group, more preferably a methyl group; R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group (preferably a methyl group), m5 in each occurrence is independently an integer of 1 to 100, preferably an integer of 1 to 20; n5, in each occurrence, is 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 of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 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 repeating units enclosed in parentheses with p5 or q5 may be present in any order; The right side is T X and T X '.] Here, X is a divalent organic group represented by the formula: A (Typically X A hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 In a preferred embodiment, X A is not substituted with these groups.

[0316] In a preferred embodiment, the X A are each independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -R 52 is a single bond, -(CH2) t5 - or an o-, m- or p-phenylene group, preferably -(CH2) t5 t5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 52 (typically R 52 hydrogen atoms) are fluorine atoms, C 1-3 Alkyl groups and C 1-3 In a preferred embodiment, R 52 is not substituted with these groups.

[0317] Preferably, the above X A are each independently single bond, C 1-20 an alkylene group, -R 51 -X 53 -R 52 -or -X 54 -R 5 - [In the formula, R 51 and R 52 has the same meaning as above, X 53 teeth, -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 have the same meaning as above, u5 represents an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 or 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.

[0318] More preferably, the above X A are each independently 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 - [In the formula, X 53 , X 54 , s5 and t5 have the same meanings as above.] is.

[0319] More preferably, the above X A are each independently single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -(CH2) t5 -or -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as above.] It could be.

[0320] In a preferred embodiment, the X A are each independently Single bond C 1-20 an alkylene group, -(CH2) s5 -X 53 -or -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 -O-, -CONR 54 - or -O-CONR 54 - and R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.

[0321] In a preferred embodiment, the X A are each independently -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [In the formula, R 54 are each independently a hydrogen atom, a phenyl group, or C 1-6 represents an alkyl group, s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.

[0322] In one embodiment, the X A are each independently single bond, C 1-20 an 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 )- [In the formula, R 53 , m5, s5, t5 and u5 are 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.

[0323] In the above formula, -(C v H 2v )- can be straight or branched chain, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, or -CH(CH3)CH2-.

[0324] Above X A are each independently a fluorine atom, C 1-3 Alkyl groups and C 1-3 Fluoroalkyl groups (preferably C1-3 In one embodiment, X may be substituted with one or more substituents selected from the group consisting of fluoroalkyl groups, perfluoroalkyl groups, and the like. A is non-substituted.

[0325] In one embodiment, X A are each independently -OC 1-6 It may be other than an alkylene group.

[0326] In another embodiment, X A Examples of the group include the following: [ka] [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 an 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 means phenyl), and [ka] (In the formula, R 42 are each independently a hydrogen atom, C 1-6 or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. is a group selected from E is -(CH2) n- (n is an integer from 2 to 6), D is the R of the molecular main chain FA1 or R FA2 E is bonded to R Si Binds to.]

[0327] Above X A Specific examples include: 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)-CH- (wherein Ph means phenyl), -CON(Ph)-(CH)- (wherein Ph means phenyl), -CON(Ph)-(CH2)3- (wherein Ph means phenyl), -CON(Ph)-(CH2)4- (wherein Ph means phenyl), -CON(Ph)-(CH2)5- (wherein Ph means phenyl), -CON(Ph)-(CH2)6- (wherein 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) 10Si(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-, [ka] , [ka] etc.

[0328] In yet another embodiment, X A are each independently a group of the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 In the formula, x1, y1, and z1 each independently represent an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the order of the repeating units enclosed in parentheses in the formula is arbitrary.

[0329] In the above formula, R 16 each independently represents an oxygen atom, phenylene, carbazolylene, or -NR 18 -(In the formula, R 18represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, R 18 is an oxygen atom or a divalent polar group.

[0330] The "divalent polar group" is not particularly limited, but examples thereof include -C(O)-, -C(=NR 19 )- and -C(O)NR 19 -(wherein R 19 represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.

[0331] In the above formula, R 17 are each independently 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 a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0332] Furthermore, the above X A The left side of each equation is R FA1 or R FA2 binds to and the right side is T X and T X '.

[0333] In yet another embodiment, X A Examples of include the following groups: [ka] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C 1-6 The alkoxy group is preferably a methyl group, each X A In the group, any number of T's may be R's in the molecular main chain.FA1 or R FA2 The following groups are attached to: -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 [ka] [In the formula, R 42 are each independently a hydrogen atom, C 1-6 or C 1-6 represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.] and some of the other Ts are Rs in the molecular backbone. Si and if present, the remaining Ts are each independently a methyl group, a phenyl group, or a C 1-6 an alkoxy group, a radical scavenger group, or an ultraviolet absorbing group.]

[0334] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, and triazines.

[0335] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0336] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include: [ka] Examples include:

[0337] In this embodiment, X A may each independently be a trivalent to decavalent group.

[0338] In yet another embodiment, X A Examples of include the following groups: [ka] [In the formula, R 25 , R 26 and R 27 are each independently a divalent to hexavalent organic group, R 25 is at least one R FA1 or R FA2 Binds to R 26 and R 27 Each has at least one R Si Binds to.]

[0339] 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 The above X is an arylene group. 58 is —O—, —S—, —CO—, —O—CO— or —COO—.

[0340] 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 at the end or in the main chain of the hydrocarbon, and preferably C 1-6 Alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-, etc. 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. 37 is N, O or S, preferably N or O. 38 -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. 46 is N, O or S, preferably O.

[0341] In this embodiment, X A may each independently be a trivalent to decavalent group.

[0342] In yet another embodiment, X A is as follows: [ka] [In the formula, X a is a single bond or a divalent organic group. It is a group represented by the following formula:

[0343] Above X a is a single bond or a divalent linking group directly bonded to the isocyanuric ring. ais 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, and 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 and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.

[0344] X a The formula is as follows: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (In the formula, X 121 ~X 124 are each independently H, F, OH, or -OSi(OR 121 ) 3 (wherein three R 121 are each independently an alkyl group having 1 to 4 carbon atoms, Above X a1 is -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 CX 121 X 122 ), x1 is an integer of 0 to 10, y1 is 0 or 1, and z1 is an integer of 1 to 10. A group represented by the following formula is more preferred.

[0345] Above X a1 is preferably —O— or —C(═O)O—.

[0346] Above X a The formula is as follows: -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - (In the formula, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.) a group represented by -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - (In the formula, m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.) a group represented by -(CF2) m17 -(CH2) m18 - (In the formula, m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.) a group represented by -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - (In the formula, m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3.) or a group represented by -(CH2) m22 - (In the formula, m22 is an integer of 1 to 3.) A group represented by the following formula is particularly preferred.

[0347] Above X a Although not particularly limited, specific examples include: -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 each independently represent an integer of 0 to 4), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- etc.

[0348] In this embodiment, XA may each independently be a divalent or trivalent group.

[0349] In one embodiment, the compound (II) represented by formula (II) does not contain a siloxane bond (—Si—O—Si—).

[0350] Compound (II) is not particularly limited, but may be 5×10 2 ~1×10 5 From the viewpoint of polymerization stability, it is preferable that the number average molecular weight of the compound (II) is 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. 19 The value is measured by F-NMR.

[0351] In one embodiment, the number average molecular weight of compound (II) may be preferably 500 or more, more preferably 1,000 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, and may be preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, even more preferably 10,000 or less, and particularly preferably 6,000 or less.

[0352] In another embodiment, the number average molecular weight of compound (II) may be preferably 4,000 or more, more preferably 5,000 or more, more preferably 6,000 or more, and may be preferably 30,000 or less, more preferably 10,000 or less.

[0353] Examples of compound (II) include compounds described in WO 2019 / 048394.

[0354] The content of the polymer compound in the TFE polymer composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.08% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, relative to the TFE polymer.

[0355] The content of the polymer compound in the TFE-based polymer composition can be determined by solid-state NMR measurement. Further, WO 2014 / 099453, WO 2010 / 075497, WO 2010 / 075496, WO 2011 / 008381, WO 2009 / 055521, WO 1987 / 007619, JP 61-293476 A, WO 2010 / 075494, WO 2010 / 075359, WO 2012 / 082454, WO 2006 / 119224, WO 2013 / 085864, Methods for measuring the content of each polymer are described in International Publication No. 2012 / 082707, International Publication No. 2012 / 082703, International Publication No. 2012 / 082451, International Publication No. 2006 / 135825, International Publication No. 2004 / 067588, International Publication No. 2009 / 068528, JP 2004-075978, JP 2001-226436, International Publication No. 1992 / 017635, International Publication No. 2014 / 069165, JP 11-181009, etc. As a method for measuring the content of the above-mentioned polymer compound, the method for measuring the content of each polymer described therein can be used.

[0356] The TFE polymer composition containing a polymer compound having an ionic group can be obtained, for example, by polymerization using the above polymer compound.

[0357] The TFE polymer composition of the present disclosure is preferably substantially free of water. This can suppress gas generation and deterioration of electrochemical device properties. Furthermore, it is advantageous in terms of production processes because a wide range of electrode active materials and solid electrolytes can be selected for combination. "Substantially free of water" means that the water content of the TFE polymer composition is 0.010% by mass or less. The water content is preferably 0.005% by mass or less, more preferably 0.003% by mass or less, even more preferably 0.002% by mass or less, and even more preferably 0.001% by mass or less. The water content is measured by the following method. The mass of the TFE-based polymer composition is measured before and after heating at 150°C for 2 hours, and the mass is calculated according to the following formula: Three samples are taken, and the calculation is carried out for each sample, and the average value is calculated and adopted. Water content (mass%)=[(mass (g) of TFE-based polymer composition before heating)−(mass (g) of TFE-based polymer composition after heating)] / (mass (g) of TFE-based polymer composition before heating)×100

[0358] The TFE-based polymer composition of the present disclosure may have a 1.0% mass loss temperature of 492°C or less. A TFE polymer composition having a 1.0% mass loss temperature of 492° C. or less can be obtained by using a hydrocarbon surfactant. The 1.0% mass loss temperature is a value measured by the following method. Approximately 10 mg of a TFE-based polymer composition that has not been heated to temperatures above 300°C is weighed out and placed in a special aluminum pan for measurement using a TG / DTA (thermogravimetric and differential thermal analyzer). The 1.0% mass loss temperature is determined as the temperature at which a 1.0 mass% weight loss occurs when the aluminum pan is heated in an air atmosphere from 25°C to 600°C at a rate of 10°C / min.

[0359] The TFE-based polymer compositions of the present disclosure may have a thermal stability index (TII) of 20 or greater. A TFE polymer composition having a TII of 20 or more can be obtained by using a hydrocarbon surfactant. The TII is preferably 25 or more, more preferably 30 or more, even more preferably 35 or more, and particularly preferably 40 or more. The TII is also preferably 50 or less. The TII is measured in accordance with ASTM D 4895-89.

[0360] The TFE polymer composition of the present disclosure has an endothermic peak temperature of preferably 333°C or higher, more preferably 335°C or higher, even more preferably 337°C or higher, and even more preferably 340°C or higher, in that it can form a mixture sheet having even greater strength, and preferably 350°C or lower, and more preferably 346°C or lower. The endothermic peak temperature is the temperature corresponding to the minimum point in the heat of fusion curve obtained by performing differential scanning calorimetry (DSC) at a heating rate of 10°C / min on a TFE-based polymer composition that has not been heated to a temperature of 300°C or higher. When there are two or more minimum points in one melting peak, each of them is regarded as an endothermic peak temperature.

[0361] The TFE polymer composition of the present disclosure has a melting point of preferably 315°C or higher, more preferably 320°C or higher, even more preferably 323°C or higher, and even more preferably 325°C or higher, in that it can form a mixture sheet having even greater strength, and preferably 335°C or lower, more preferably 330°C or lower. The melting point is the temperature corresponding to the minimum point in the heat of fusion curve obtained by subjecting a TFE-based polymer composition that has been heated to a temperature of 300°C or higher to differential scanning calorimetry (DSC) at a heating rate of 10°C / min.

[0362] 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, even more preferably 2.220 or less, even more preferably 2.200 or less, even more preferably 2.190 or less, especially preferably 2.180 or less, and particularly preferably 2.170 or less, in that a composite sheet having even greater strength can be formed. The SSG is preferably 2.130 or more, and may be 2.140 or more, or may be 2.150 or more. The SSG is measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895 89.

[0363] The form of the TFE-based polymer composition of the present disclosure is not limited, but is preferably a powder, since it can be mixed with an electrode active material and a solid electrolyte without using a large amount of a dispersion medium. The TFE polymer composition may be in a form other than a powder, for example, a dispersion.

[0364] The TFE polymer composition of the present disclosure can be suitably produced, for example, by a production method including a step (A) of preparing an aqueous dispersion of a TFE polymer, a step (B) of coagulating the aqueous dispersion to obtain a wet powder, and a step (C) of drying the wet powder.

[0365] The step (A) is preferably, for example, a step (A1) of obtaining an aqueous dispersion of a TFE-based polymer by emulsion polymerizing TFE in an aqueous medium in the presence of an anionic fluorine-containing surfactant.

[0366] The emulsion polymerization in step (A1) can be carried out by a known method. For example, an aqueous dispersion containing particles (primary particles) of the TFE-based polymer can be obtained by emulsion polymerization of monomers necessary for constituting the TFE-based polymer in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator. In the emulsion polymerization, a chain transfer agent, a buffer, a pH adjuster, a stabilizing aid, a dispersion stabilizer, a radical scavenger, etc. may be used as necessary.

[0367] The 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. The emulsion polymerization can be carried out by charging an aqueous medium, the anionic fluorine-containing surfactant, monomers, and other additives as necessary into a polymerization reactor, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of polymerization initiator to initiate the polymerization reaction. After the start of the polymerization reaction, monomers, polymerization initiator, chain transfer agent, the surfactant, etc. may be additionally added depending on the purpose.

[0368] The polymerization initiator is not particularly limited as long as it can generate radicals within the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, polymerization can also be initiated as a redox reaction in combination with a reducing agent or the like. The concentration of the polymerization initiator is determined appropriately depending on the type of monomer, the molecular weight of the target TFE-based polymer, and the reaction rate.

[0369] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0370] The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl peroxycarbonates 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, and the like. Also usable are di(ω-hydro-dodecafluoroheptanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di(ω-chloro Representative examples include di[perfluoro(or fluorochloro)acyl]peroxides such as di(ω-hexafluorobutyryl)peroxide, di(ω-chloro-decafluorohexanoyl)peroxide, di(ω-chloro-tetradecafluorooctanoyl)peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl)peroxide, di(trichlorooctafluorohexanoyl)peroxide, di(tetrachloroundecafluorooctanoyl)peroxide, di(pentachlorotetradecafluorodecanoyl)peroxide, and di(undecachlorodotriacontafluorodocosanoyl)peroxide.

[0371] The water-soluble radical polymerization initiator may be a known water-soluble peroxide, such as ammonium salts, potassium salts, or sodium salts of persulfuric acid, perborate, perchloric acid, perphosphoric acid, or percarbonate, t-butyl permaleate, t-butyl hydroperoxide, or disuccinic acid peroxide. Among these, ammonium persulfate and disuccinic acid peroxide are preferred. A reducing agent such as sulfites or sulfites may also be contained, and the amount used may be 0.1 to 20 times the amount of the peroxide.

[0372] The amount of the water-soluble radical polymerization initiator to be added is not particularly limited, but may be added all at once, stepwise, or continuously at the beginning of the polymerization in an amount (for example, several ppm relative to the water concentration) that does not significantly decrease the polymerization rate. The upper limit is a range in which the reaction temperature can be increased while removing heat from the equipment using the heat of polymerization reaction, and a more preferred upper limit is a range in which the heat of polymerization reaction can be removed from the equipment. In terms of easily obtaining the above-mentioned physical properties, the amount of the polymerization initiator added is preferably an amount corresponding to 0.1 ppm or more, more preferably an amount corresponding to 1.0 ppm or more, and is preferably an amount corresponding to 100 ppm or less, more preferably an amount corresponding to 10 ppm or less, relative to the aqueous medium.

[0373] For example, when polymerization is carried out at low temperatures below 30°C, it is preferable to use a redox initiator, which combines an oxidizing agent and a reducing agent, as the polymerization initiator. Examples of oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, and bromates. Examples of reducing agents include sulfites, bisulfites, bromates, diimines, and oxalic acid. Examples of persulfates include ammonium persulfate and potassium persulfate. Examples of sulfites include sodium sulfite and ammonium sulfite. To increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the redox initiator combination. Examples of copper salts include copper(II) sulfate, and examples of iron salts include iron(II) sulfate.

[0374] As the redox initiator, it is preferred that the oxidizing agent is permanganic acid or a salt thereof, a persulfate, manganese triacetate, a cerium (IV) salt, or bromic acid or a salt thereof, and the reducing agent is a dicarboxylic acid or a salt thereof, or a diimine. More preferably, the oxidizing agent is permanganic acid or a salt thereof, persulfate, or bromic acid or a salt thereof, and the reducing agent is a dicarboxylic acid or a salt thereof.

[0375] Examples of the redox initiator include combinations of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, manganese triacetate / oxalic acid, manganese triacetate / ammonium oxalate, cerium ammonium nitrate / oxalic acid, and cerium ammonium nitrate / ammonium oxalate. When a redox initiator is used, either the oxidizing agent or the reducing agent may be charged into a polymerization vessel in advance, and then the other may be added continuously or intermittently to initiate polymerization. For example, when potassium permanganate / oxalic acid is used, it is preferable to charge oxalic acid into a polymerization vessel and then continuously add potassium permanganate thereto. In this specification, when the redox initiator is described as "potassium permanganate / oxalic acid," it means a combination of potassium permanganate and oxalic acid. The same applies to other compounds.

[0376] 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 the salt is more preferably at least one selected from the group consisting of persulfates, permanganates, cerium (IV) salts, and bromates, further preferably permanganates, and particularly preferably potassium permanganate. Furthermore, the reducing agent which is the salt is more preferably at least one selected from the group consisting of oxalate, malonate, succinate, glutarate and bromate, further preferably oxalate, and particularly preferably ammonium oxalate.

[0377] Specifically, the redox initiator is preferably 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 cerium ammonium nitrate / ammonium oxalate, more preferably at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, and cerium ammonium nitrate / ammonium oxalate, and even more preferably potassium permanganate / oxalic acid.

[0378] When a redox initiator is used, the oxidizing agent and the reducing agent may be added all at once at the beginning of the polymerization, or the reducing agent may be added all at once at the beginning of the polymerization and the oxidizing agent may be added continuously, or the oxidizing agent may be added all at once at the beginning of the polymerization and the reducing agent may be added continuously, or both the oxidizing agent and the reducing agent may be added continuously.

[0379] When one of the redox polymerization initiators is added at the beginning of the polymerization and the other is added continuously, the rate of addition is preferably gradually reduced in order to obtain a TFE-based polymer having a low SSG, and further, the addition is preferably stopped midway through the polymerization, preferably before 20 to 40% by mass of the total TFE consumed in the polymerization reaction is consumed.

[0380] When a redox initiator is used as a polymerization initiator, the amount of oxidizing agent added to the aqueous medium is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, even more preferably 0.5 ppm or more, even more preferably 1 ppm or more, particularly preferably 5 ppm or more, particularly preferably 10 ppm or more, and preferably 10,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 100 ppm or less, and even more preferably 50 ppm or less. The amount of reducing agent added is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, even more preferably 3 ppm or more, even more preferably 5 ppm or more, particularly preferably 10 ppm or more, and preferably 10,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 100 ppm or less, and even more preferably 50 ppm or less. When a redox initiator is used in the emulsion polymerization, the polymerization temperature is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower. The polymerization temperature is preferably 10° C. or higher, more preferably 20° C. or higher, and even more preferably 30° C. or higher.

[0381] As the polymerization initiator, a water-soluble radical polymerization initiator and a redox initiator are preferred, since the above-mentioned properties can be easily obtained.

[0382] The aqueous medium is a reaction medium for polymerization and refers to a liquid containing water. The 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 an alcohol, ether, or ketone, and / or a fluorine-containing organic solvent having a boiling point of 40° C. or lower.

[0383] In the emulsion polymerization, a nucleating agent, a chain transfer agent, a buffer, a pH adjuster, a stabilizing aid, a dispersion stabilizer, a radical scavenger, a decomposing agent for the polymerization initiator, a dicarboxylic acid, etc. may be used, if necessary.

[0384] The emulsion polymerization is preferably carried out with the addition of a nucleating agent for the purpose of adjusting the particle size, and the nucleating agent is preferably added before the start of the polymerization reaction. As the nucleating agent, known agents can be used, and for example, at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents is preferred, and a nonionic surfactant is more preferred.

[0385] The fluoropolyether may, for example, be a perfluoropolyether (PFPE) acid or a salt thereof. The perfluoropolyether (PFPE) acid or salt thereof may have any 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. 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

[0386] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed therein, the PFPE acid or its salt may have a carboxylic acid group or a salt thereof at one or both ends. The PFPE acid or its salt may also have a sulfonic acid or phosphonic acid group or a salt thereof at one or both ends. The PFPE acid or its salt may also have a different group at each end. For monofunctional PFPEs, 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, and 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 2 or 3 carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. Also preferably, the PFPE acid or salt thereof 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 PFPE acids or salts thereof having acid groups at one or both termini can be used in the manufacturing method of the present disclosure. The PFPE acid or salt thereof preferably has a number average molecular weight of less than 6000 g / mol.

[0387] The emulsion polymerization is preferably carried out with the addition of a radical scavenger or a decomposer for the polymerization initiator, since this allows the TFE polymer to have a higher molecular weight and improves the strength of the mixture sheet.The radical scavenger or decomposer for 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 preferably before 50% by mass or less, preferably 40% by mass or less is polymerized.When depressurization and repressurization are performed as described below, it is preferable to add it after that.

[0388] The radical scavenger is a compound that does not have the ability to restart after addition or chain transfer to a free radical in the polymerization system. Specifically, a compound that easily undergoes a chain transfer reaction with a primary radical or a propagating radical to generate a stable radical that does not subsequently react with the monomer, or a compound that easily undergoes an addition reaction with a primary radical or a propagating radical to generate a stable radical, is used. Generally, the activity of what is called a chain transfer agent is characterized by the chain transfer constant and the reinitiation efficiency, but among chain transfer agents, those with a reinitiation efficiency of almost 0% are called radical scavengers. The radical scavenger can also be described as a compound whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant and whose reinitiation efficiency is substantially zero percent. "Reinitiation efficiency is substantially zero percent" means that the generated radicals turn the radical scavenger into stable radicals. Preferably, the compound has a chain transfer constant (Cs) with TFE at the polymerization temperature (=chain transfer rate constant (kc) / polymerization rate constant (kp)) of more than 0.1, and the compound has a chain transfer constant (Cs) of more preferably 0.5 or more, even more preferably 1.0 or more, even more preferably 5.0 or more, and particularly preferably 10 or more.

[0389] The radical scavenger is preferably at least one selected from the group consisting of, for example, aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl). Examples of aromatic hydroxy compounds include unsubstituted phenol, polyhydric phenol, salicylic acid, m- or p-salicylic acid, gallic acid, and naphthol. Examples of the unsubstituted phenol include o-, m-, or p-nitrophenol, o-, m-, or p-aminophenol, p-nitrosophenol, etc. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, naphthresorcinol, etc. Examples of aromatic amines include o-, m-, or p-phenylenediamine, benzidine, and the like. Examples of the quinone compound include o-, m-, or p-benzoquinone, 1,4-naphthoquinone, and alizarin. Examples of thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN). Of the above radical scavengers, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

[0390] The amount of the radical scavenger added is preferably an amount equivalent to 3 to 500% (molar basis) of the polymerization initiator concentration, from the viewpoint of appropriately reducing the standard specific gravity. A more preferred lower limit is 10% (molar basis), and even more preferred is 15% (molar basis). A more preferred upper limit is 400% (molar basis), and even more preferred is 300% (molar basis).

[0391] The polymerization initiator decomposer may be any compound capable of decomposing the polymerization initiator used, and is preferably at least one selected from the group consisting of sulfites, bisulfites, bromates, diimines, diimine salts, oxalic acid, oxalates, copper salts, and iron salts. Examples of sulfites include sodium sulfite and ammonium sulfite. Examples of copper salts include copper(II) sulfate, and examples of iron salts include iron(II) sulfate. The amount of the decomposing agent added is preferably an amount equivalent to 3 to 500% (molar basis) of the initiator concentration, from the viewpoint of appropriately reducing the standard specific gravity. A more preferred lower limit is 10% (molar basis), and even more preferred is 15% (molar basis). A more preferred upper limit is 400% (molar basis), and even more preferred is 300% (molar basis).

[0392] The emulsion polymerization may be carried out in the presence of 5 to 500 ppm of dicarboxylic acid relative to the aqueous medium, preferably 10 to 200 ppm, in order to reduce the amount of coagulation produced during polymerization. If the amount of dicarboxylic acid relative to the aqueous medium is too small, sufficient effects may not be obtained, while if the amount is too large, a chain transfer reaction may occur, resulting in a low molecular weight polymer. The amount of dicarboxylic acid is more preferably 150 ppm or less. The dicarboxylic acid may be added before the start of the polymerization reaction or during the polymerization.

[0393] The dicarboxylic acid is preferably, for example, one represented by the general formula: HOOCRCOOH (wherein R represents an alkylene group having 1 to 5 carbon atoms), more preferably succinic acid, malonic acid, glutaric acid, adipic acid, or pimelic acid, and even more preferably succinic acid.

[0394] In the emulsion polymerization, the polymerization temperature and polymerization pressure are appropriately determined depending on the type of monomer used, the molecular weight of the target TFE 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, the polymerization temperature is more preferably 120°C or lower, and even more preferably 100°C or lower. The polymerization pressure is 0.05 to 10 MPaG. The polymerization pressure is more preferably 0.3 MPaG or more, and even more preferably 0.5 MPaG or more. The polymerization pressure is more preferably 5.0 MPaG or less, and even more preferably 3.0 MPaG or less.

[0395] When VDF is used as the modifying monomer, 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, more preferably 0.01 mol% or more, in order to easily obtain the above-mentioned physical properties in the emulsion polymerization. The concentration may also 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 VDF concentration may be maintained until the end of the polymerization reaction, or pressure may be released during the reaction. VDF is preferably charged all at once before the start of polymerization, but a portion may be added continuously or intermittently after the start of polymerization.

[0396] When VDF is used as the modifying monomer, it is preferable not to release the pressure in the emulsion polymerization after VDF is charged into the polymerization vessel until the polymerization is completed, which allows VDF to remain in the system until the end of the polymerization, thereby further increasing the strength of the resulting mixture sheet using the TFE-based polymer.

[0397] When HFP is used as the modifying monomer, 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 % in the emulsion polymerization, since this facilitates the attainment of the above-mentioned physical properties. Furthermore, the HFP concentration in the gas in the reactor at the time when 40 mass % of the total TFE consumed in the polymerization reaction has been polymerized is preferably greater than 0 mol % and 0.2 mol % or less. The above HFP concentration is preferably maintained thereafter until the end of the polymerization reaction. HFP may be charged all at once before the start of polymerization, or a portion may be charged before the start of polymerization and then added continuously or intermittently after the start of polymerization. By allowing HFP to remain until the end of the polymerization reaction, the extrusion pressure is reduced, despite the high strength of the resulting composite sheet using the TFE-based polymer.

[0398] When HFP is used as the modifying monomer, in the above emulsion polymerization, it is preferable to release the pressure before 5 to 40 mass% of the total TFE consumed in the polymerization reaction is polymerized, and then re-increase the pressure using only TFE, in order to further improve the strength of the resulting mixture sheet using the TFE-based polymer. The pressure reduction is preferably carried out so that the pressure inside the reactor becomes 0.2 MPaG or less, more preferably 0.1 MPaG or less, and even more preferably 0.05 MPaG or less, and is preferably carried out so that the pressure inside the reactor becomes 0.0 MPaG or more. The depressurization and re-pressurization may be repeated several times. The depressurization may be carried out until the pressure is reduced using a vacuum pump.

[0399] When CTFE is used as the modifying monomer, in the emulsion polymerization, 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, more preferably 0.01 mol% or more, since this facilitates the attainment of the above-mentioned physical properties. The concentration is also preferably 3.0 mol% or less, more preferably 1.0 mol% or less. The CTFE concentration may be maintained until the end of the polymerization reaction, or pressure may be released during the reaction. CTFE is preferably charged all at once before the start of polymerization, but a portion may be added continuously or intermittently after the start of polymerization.

[0400] When CTFE is used as the modified monomer, it is preferable not to release the pressure in the emulsion polymerization after the CTFE is charged into the polymerization vessel until the polymerization is completed, which allows the CTFE to remain in the system until the end of the polymerization, and further increases the strength of the resulting mixture sheet using the TFE-based polymer.

[0401] 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.

[0402] In the hydrocarbon surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0403] Step (A2) preferably comprises a step of carrying out emulsion polymerization of tetrafluoroethylene alone, or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with 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.

[0404] The continuous addition of a specific hydrocarbon surfactant means, for example, adding the specific hydrocarbon surfactant over time, without interruption, or in portions, rather than all at once. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) that has been subjected to radical treatment or oxidation treatment. The radical treatment may be any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). For example, the radical treatment may involve adding deionized water and a hydrocarbon surfactant to a reactor, sealing the reactor, replacing the system with nitrogen, heating and pressurizing the reactor, adding a polymerization initiator, stirring for a certain period of time, and then depressurizing the reactor to atmospheric pressure and cooling. The oxidation treatment is a treatment in which an oxidizing agent is added to a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). Examples of oxidizing agents include oxygen, ozone, hydrogen peroxide, manganese (IV) oxide, potassium permanganate, potassium dichromate, nitric acid, and sulfur dioxide. The production method described above makes it possible to produce a TFE 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.

[0405] In the above production method, the step of continuously adding the specific hydrocarbon surfactant preferably starts adding the hydrocarbon surfactant to the aqueous medium when the solid content of the TFE polymer formed in the aqueous medium is less than 0.60% by mass. It is preferable to start adding the specific hydrocarbon surfactant to the aqueous medium when it is 0.5% by mass or less. It is more preferable to start adding the specific hydrocarbon surfactant when the solid content is 0.3% by mass or less, even more preferably when it is 0.2% by mass or less, even more preferably when it is 0.1% by mass or less, and it is particularly preferable to start adding it at the start of polymerization. The solid content is the concentration relative to the total of the aqueous medium and the TFE polymer.

[0406] In the step of continuously adding the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant added is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium, more preferably 0.05% by mass at the lower limit, even more preferably 0.1% by mass at the lower limit, more preferably 5% by mass at the upper limit, and even more preferably 1% by mass at the upper limit.

[0407] In a process for emulsion polymerization of tetrafluoroethylene alone or tetrafluoroethylene and a modified monomer copolymerizable with tetrafluoroethylene in an aqueous medium in the presence of the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant is preferably large, preferably 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferred lower limit is 0.001% by mass, and a more preferred upper limit is 1% by mass. If the amount is less than 0.0001% by mass, the dispersion force may be insufficient, while if the amount exceeds 10% by mass, the effect commensurate with the amount may not be obtained, and instead, the polymerization rate may decrease or the reaction may stop. The amount of the specific hydrocarbon surfactant is determined appropriately depending on the type of monomer used, the molecular weight of the target TFE polymer, and other factors.

[0408] The specific hydrocarbon surfactants include those represented by the formula: RX (wherein R is a fluorine-free organic group having 1 to 2000 carbon atoms and one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), and X is -OSOX 1 , -COOX 1 or -SO3X 1 (X 1 is H, metal atom, NR 1 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 1 is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. )) is preferred. R preferably has 500 or less carbon atoms, more preferably 100 or less, even more preferably 50 or less, and even more preferably 30 or less. The specific hydrocarbon surfactant is a surfactant represented by the following formula (a): [ka] (In the formula, R 1a R is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond (preferably an organic group not containing fluorine), and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2a and R 3a R is independently a single bond or a divalent linking group. 1a , R 2a and R 3a X has a total of 6 or more carbon atoms. a is H, metal atom, NR 4a 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4aR is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 1a , R 2a and R 3a Any two of these may be bonded to each other to form a ring.) A surfactant (a) represented by the following formula (b): [ka] (In the formula, R 1b 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 the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. 2b and R 4b are independently H or a substituent. 3b is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. X b is H, metal atom, NR 5b 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5b R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 1b , R 2b , R 3b and R 4b Any two of may be bonded to each other to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b represents H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents -OSO3X in the formula. b(b) a surfactant represented by the following formula (c): [ka] (In the formula, R 1c R is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond (preferably an organic group not containing fluorine), and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2c and R 3c R is independently a single bond or a divalent linking group. 1c , R 2c and R 3c A has a total of 5 or more carbon atoms. c -COOX c or -SO3X c (X c is H, metal atom, NR 4c 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4c R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 1c , R 2c and R 3c Any two of these may be bonded to each other to form a ring.) A surfactant (c) represented by the following formula (d): [ka] (In the formula, R 1d 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 the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. 2d and R 4d are independently H or a substituent. 3dis an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. A d -SO3X d or -COOX d (X d is H, metal atom, NR 5d 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5d R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 1d , R 2d , R 3d and R 4d Any two of may be bonded to each other to form a ring. 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 The carbonyl group contained in CO-B- is excluded.) 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. * represents A in the formula. d and a surfactant (d) represented by the following formula (e): [ka] (In the formula, R 1e ~R 5e represents H or a monovalent substituent, provided that R 1e and R 3e At least one of the groups has the general formula: -Y e -R 6e a group represented by R 2e and R 5e At least one of the groups has the general formula: -X e -A e or a group represented by the general formula: -Y e -R 6erepresents a group represented by the following formula: Also, X e is the same or different in each occurrence and is a divalent linking group or bond; A e may be the same or different in each occurrence, -COOM e , -SO3M e or -OSO3M e (M e is H, metal atom, NR 7e 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7e is H or an organic group (preferably a fluorine-free organic group); Y e are the same or different in each occurrence, and are -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e - and -NR 8e a divalent linking group selected from the group consisting of CO—, or a bond, R 8e is H or an organic group (preferably a fluorine-free organic group); R 6e are the same or different in each occurrence and each represents an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms; Represents. R 1e ~R 5e Any two of the groups may be bonded to each other to form a ring.)

[0409] The surfactant (a) will now be described.

[0410] 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 three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. In other words, acyl groups such as an acetyl group represented by CH3-C(=O)- are also included in the alkyl group. Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1a In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0411] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocycle. For example, a group represented by CH3-C(=O)-CH2- has 3 carbon atoms, a group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and a group represented by CH3-C(=O)- has 2 carbon atoms.

[0412] In the alkyl group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferable that the alkyl group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 101a (In the formula, R 101a is an alkyl group). The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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.

[0413] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group. R 2a and R 3a are preferably independently a single bond, a linear or branched alkylene group having one or more carbon atoms, or a cyclic alkylene group having three or more carbon atoms. R 2a and R 3a The alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0414] In the alkylene group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferable that the alkylene group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 102a (In the formula, R 102a is an alkyl group). The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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.

[0415] R 1a , R 2a and R 3ahas a total carbon number of 6 or more. The total carbon number is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. R 1a , R 2a and R 3a Any two of these may be bonded to each other to form a ring.

[0416] In formula (a), X a is H, metal atom, NR 4a 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4a is H or an organic group (preferably an organic group not containing fluorine). 4a may be the same or different. 4a The organic group in R is preferably an alkyl group. 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. X a H, alkali metals (group 1), alkaline earth metals (group 2) or NR 4a X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. a When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0417] R 1aAs the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or an alkyl group containing a monovalent or divalent heterocycle having 3 to 45 carbon atoms is preferred.

[0418] Examples of surfactant (a) include the following surfactants: a is as described above.

[0419] [ka]

[0420] [ka]

[0421] [ka]

[0422] [ka]

[0423] [ka]

[0424] [ka]

[0425] [ka]

[0426] [ka]

[0427] The surfactant (a) can be produced, for example, by the production method described in WO 2020 / 022355.

[0428] Next, the surfactant (b) will be described.

[0429] 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 alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1b In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0430] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0431] R 1b The substituent that the alkyl group may have is preferably 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, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0432] R 1b The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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 alkyl group preferably does not have any substituents.

[0433] R 1b As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0434] In formula (b), R 2b and R 4b are independently H or a substituent. 2b and R 4b may be the same or different.

[0435] R 2b and R 4b The substituent as is preferably 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, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0436] R 2b and R 4b The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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 alkyl group preferably does not have any substituents.

[0437] R 2b and R 4b The alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0438] R 2b and R 4b are each independently preferably H or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not containing a substituent, even more preferably H, a methyl group (-CH3), or an ethyl group (-C2H5), and particularly preferably H.

[0439] In formula (b), R 3b R is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3b When there are a plurality of, they may be the same or different.

[0440] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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.

[0441] 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, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and still more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0442] R 1b , R 2b , R 3b and R 4b Any two of may be bonded to each other to form a ring, but it is preferable that they do not form a ring.

[0443] In formula (b), n is an integer of 1 or greater. 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.

[0444] In formula (b), p and q are independently an integer of 0 or greater. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0445] The sum of n, p, and q is preferably an integer of 5 or greater. The sum of n, p, and q is more preferably an integer of 8 or greater. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and even more preferably an integer of 40 or less.

[0446] In formula (b), X b is H, metal atom, NR 5b 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5b is H or an organic group (preferably an organic group not containing fluorine). 5b may be the same or different. 5b The organic group in R is preferably an alkyl group. 5b 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. X b is a metal atom or NR 5b 4(R 5b is as above). X b H, alkali metals (group 1), alkaline earth metals (group 2) or NR 5b X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. b When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0447] In formula (b), L represents a single bond, -CO2-B-*, -OCO-B-*, or -CONR 6b -B-*, -NR 6bCO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b The carbonyl group contained in CO-B- is excluded.) 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 alkylene group preferably has 1 to 5 carbon atoms. 6b is preferably H or a methyl group. * represents -OSO3X in the formula. b This refers to the side that binds to the

[0448] L is preferably a single bond.

[0449] The surfactant (b) may be a compound represented by the following formula: [ka] (In the formula, R 1b , R 2b , L, n and X b is as described above. ) is preferred.

[0450] 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)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Naぁ 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ぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Liぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ 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, Examples include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na.

[0451] The surfactant (b) can be produced, for example, by the production method described in WO 2020 / 022355.

[0452] Next, the surfactant (c) will be described.

[0453] 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 alkyl group has three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. In other words, acyl groups such as an acetyl group represented by CH3-C(=O)- are also included in the alkyl group. Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1c In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0454] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocycle. For example, a group represented by CH3-C(=O)-CH2- has 3 carbon atoms, a group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and a group represented by CH3-C(=O)- has 2 carbon atoms.

[0455] In the alkyl group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferable that the alkyl group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 101c (In the formula, R 101c is an alkyl group). The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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.

[0456] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group. R 2c and R 3c are 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 2c and R 3c The alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0457] In the alkylene group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferable that the alkylene group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 102c (In the formula, R 102c is an alkyl group). The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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.

[0458] R 1c , R 2c and R 3c has a total carbon number of 5 or more. The total carbon number is preferably 7 or more, more preferably 9 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. R 1c , R 2c and R 3c Any two of these may be bonded to each other to form a ring.

[0459] In formula (c), in formula, A c -COOX c or -SO3X c (X c is H, metal atom, NR 4c 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4c R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 4c The organic group in R is preferably an alkyl group. 4cis 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. X c H, alkali metals (group 1), alkaline earth metals (group 2) or NR 4c X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. c When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0460] R 1c As the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or an alkyl group containing a monovalent or divalent heterocycle having 3 to 45 carbon atoms is preferred.

[0461] Examples of the surfactant (c) include the following surfactants: c is as described above.

[0462] [ka]

[0463] [ka]

[0464] [ka]

[0465] [ka]

[0466] [ka]

[0467] [ka]

[0468] [ka]

[0469] [ka]

[0470] The surfactant (c) can be produced, for example, by the production method described in WO 2020 / 022355.

[0471] Next, the surfactant (d) will be described.

[0472] 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. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1d In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0473] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0474] R 1d The substituent that the alkyl group may have is preferably 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, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0475] R 1d The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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 alkyl group preferably does not have any substituents.

[0476] R 1d As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0477] In formula (d), R 2d and R 4d are independently H or a substituent. 2d and R 4d may be the same or different.

[0478] R 2d and R 4d The substituent as is preferably 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, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0479] R 2d and R 4d The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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 alkyl group preferably does not have any substituents.

[0480] R 2d and R 4d The alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0481] R 2d and R 4d are each independently preferably H or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not containing a substituent, even more preferably H, a methyl group (-CH3), or an ethyl group (-C2H5), and particularly preferably H.

[0482] In formula (d), R 3dR is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3d When there are a plurality of, they may be the same or different.

[0483] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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.

[0484] 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, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and still more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0485] R 1d , R 2d , R 3d and R 4d Any two of these may be bonded to each other to form a ring.

[0486] In formula (d), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and even more preferably an integer of 5 to 25.

[0487] In formula (d), p and q are independently an integer of 0 or greater. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0488] The sum of n, p, and q is preferably an integer of 6 or greater. The sum of n, p, and q is more preferably an integer of 8 or greater. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and even more preferably an integer of 40 or less.

[0489] In formula (d), A d -SO3X d or -COOX d (X d is H, metal atom, NR 5d 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5d R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 5d The organic group in R is preferably an alkyl group. 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. X d is a metal atom or NR 5d 4(R 5d is as above). X d H, alkali metals (group 1), alkaline earth metals (group 2) or NR 5d X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. dWhen is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0490] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, or -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) 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 alkylene group more preferably has 1 to 5 carbon atoms. 6d is more preferably H or a methyl group. d This refers to the side that binds to the

[0491] L is preferably a single bond.

[0492] Examples of the 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ぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2SO3Naぁ CH3C(O)CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Naぁ 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.

[0493] The surfactant (d) can be produced, for example, by the production method described in WO 2020 / 022355.

[0494] Next, the surfactant (e) will be described.

[0495] In formula (e), R 1e ~R 5e represents H or a monovalent substituent, provided that R 1e and R 3e At least one of the groups has the general formula: -Y e -R 6e a group represented by R 2e and R 5e At least one of the groups has the general formula: -X e -A e or a group represented by the general formula: -Ye -R 6e R represents a group represented by 1e ~R 5e Any two of these may be bonded to each other to form a ring.

[0496] R 1e The substituent that the alkyl group may have is preferably 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, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0497] R 1e The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon 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 alkyl group preferably does not have any substituents.

[0498] R 1e As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0499] The monovalent substituent includes a group represented by the general formula: -Y e -R 6e a group represented by the general formula: -X e -A ea group represented by the formula: -H, optionally substituted C 1-20 Alkyl groups, -NH2, -NHR 9e (R 9e represents an organic group (preferably a fluorine-free organic group), -OH, -COOR 9e (R 9e is an organic group (preferably a fluorine-free organic group) or -OR 9e (R 9e is preferably an organic group (preferably an organic group not containing fluorine). The alkyl group preferably has 1 to 10 carbon atoms.

[0500] R 9e As for C 1-10 or C 1-10 The alkylcarbonyl group of C is preferred. 1-4 or C 1-4 An alkylcarbonyl group of the formula is more preferred.

[0501] In the formula, X e represents, the same or different in each occurrence, a divalent linking group or bond. R 6e 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.

[0502] X e Examples include -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, and -CONR 8e - and -NR 8e a divalent linking group containing at least one bond selected from the group consisting of CO—, C 1-10 An alkylene group or a bond represented by the formula R 8e represents H or an organic group (preferably an organic group not containing fluorine).

[0503] R 8e The organic group in R is preferably an alkyl group. 8eAs for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0504] In formula (e), A e may be the same or different in each occurrence, -COOM e , -SO3M e or -OSO3M e (M e is H, metal atom, NR 7e 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7e is H or an organic group (preferably an organic group not containing fluorine). 7e may be the same or different. In formula (e), A e Ha-COOM e This is one of the preferred embodiments.

[0505] R 7e The organic group in R is preferably an alkyl group. 7e As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the formula: The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li.

[0506] M e The group may be 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 preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0507] In formula (e), Y eare the same or different in each occurrence, and are -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e - and -NR 8e a divalent linking group selected from the group consisting of CO—, or a bond, R 8e represents H or an organic group (preferably an organic group not containing fluorine).

[0508] Y e Examples include bonds, -O-, -COO-, -OCO-, and -CONR. 8e - and -NR 8e A divalent linking group selected from the group consisting of -CO- is preferred, and a divalent linking group selected from the group consisting of a bond, -COO-, and -OCO- is more preferred.

[0509] R 8e The organic group in R is preferably an alkyl group. 8e As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0510] In formula (e), R 6e In each occurrence, R may be the same or different and represent an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms. 6e The organic group (preferably an organic group containing no fluorine) preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0511] R 6e The alkyl group of R may contain one or more groups selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms, but does not contain these groups at the terminal of the alkyl group. 6eIn the alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0512] R 6e As for 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 or a group represented by 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). 10e is an alkylene group, R 11e is preferably an alkyl group which may have a substituent. R 6e As the general formula: -R 10e -CO-R 11e A group represented by the following formula is more preferred.

[0513] R 8e The organic group in R is preferably an alkyl group. 8e As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0514] R 10eThe number of carbon atoms in the alkylene group of R is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. 10e The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0515] R 11e The number of carbon atoms in the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 6, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. 11e The alkyl group of R is preferably composed of only primary, secondary, and tertiary carbon atoms, and particularly preferably composed of only primary and secondary carbon atoms. 11e As the alkyl group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, and a methyl group is most preferred.

[0516] In formula (e), R 2e and R 5e At least one of the groups has the general formula: -X e -A e and A is a group represented by the formula: e Ha-COOM e In one preferred embodiment,

[0517] As the surfactant (e), a compound represented by general formula (e-1), a compound represented by general formula (e-2), or a compound represented by general formula (e-3) is preferred, and a compound represented by general formula (e-1) or a compound represented by general formula (e-2) is more preferred.

[0518] General formula (e-1): [ka] (In the formula, R 3e ~R 6e , X e , A e and Y eis as above.)

[0519] General formula (e-2): [ka] (In the formula, R 4e ~R 6e , X e , A e and Y e is as above.)

[0520] General formula (e-3): [ka] (In the formula, R 2e , R 4e ~R 6e , X e , A e and Y e is as above.)

[0521] General formula:-X e -A e Examples of the group represented by the formula: -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 -SO3Me , -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 mentioned above, R 12e is C 1-10 An alkylene group represented by the formula: is preferred. Above R 12e In the alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0522] General formula:-Y e -R 6e Examples of the group represented by the formula: General formula:-R 10e -CO-R 11e a group represented by General formula:-OCO-R 10e -CO-R 11e a group represented by General formula:-COO-R 10e -CO-R 11e a group represented by 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 or a group represented by General formula:-CONR 8e -R 10e -NR 8e CO-R 11e A group represented by (In the formula, R 8e , R 10e and R 11e is as described above.) is preferred.

[0523] In the formula, R 4e and R 5e are independently H or C 1-4 The alkyl groups are preferably: Above R 4e and R 5e In the alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0524] R in general formula (e-1) 3e is H or optionally substituted C 1-20 The alkyl group is preferably H or unsubstituted C 1-20 An alkyl group represented by the formula (I) is more preferred, and H is even more preferred. Above R3e In the alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0525] R in general formula (e-3) 2e is H, OH or optionally substituted C 1-20 The alkyl group having no H, OH or substituent is preferably C 1-20 An alkyl group such as the above is more preferred, and H or OH is even more preferred. Above R 2e In the alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0526] The surfactant (e) can be produced by a known production method.

[0527] The specific hydrocarbon surfactant is preferably a carboxylic acid type hydrocarbon surfactant. The 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 with an inorganic cation (for example, a metal atom, ammonium, etc.), and for example, from among the specific hydrocarbon surfactants described above, a hydrocarbon surfactant having a carboxyl group or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation can be used. In the above-mentioned carboxylic acid type hydrocarbon surfactant, the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0528] The carboxylic acid type hydrocarbon surfactant is preferably at least one selected from the group consisting of surfactants (c) represented by the above formula (c) and surfactants (d) represented by the above formula (d), which have a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.).

[0529] It is also preferable that the specific hydrocarbon surfactant is a sulfonic acid hydrocarbon surfactant. The sulfonic acid hydrocarbon surfactant is not limited as long as it has a -SO3H group, a -OSO3H group, or a group in which the hydrogen atom of these groups is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.). For example, from the specific hydrocarbon surfactants described above, a hydrocarbon surfactant having a -SO3H group, a -OSO3H group, or a group in which the hydrogen atom of these groups is substituted with an inorganic cation can be used. In the sulfonic acid type hydrocarbon surfactant, the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0530] The TFE polymer composition of the present disclosure can be efficiently produced by using at least one of the specific hydrocarbon surfactants. The TFE 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 other surfactant compounds other than the specific hydrocarbon surfactants, as long as they are volatile or may remain in a molded product or the like made of a TFE polymer.

[0531] As the other compounds having surface activity, for example, those described in JP-A Nos. 2013-542308, 2013-542309, and 2013-542310 can be used.

[0532] Other surface-active compounds may be surfactants having a hydrophilic portion and a hydrophobic portion on the same molecule, such as hydrocarbon surfactants, which may be cationic, nonionic, or anionic. In the above compound, the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0533] Cationic surfactants typically have a positively charged hydrophilic portion, such as an alkylated ammonium halide, such as an alkylated ammonium bromide, and a hydrophobic portion, such as a long-chain fatty acid. In the cationic surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0534] Anionic surfactants typically have a hydrophilic portion, such as a carboxylate, sulfonate, or sulfate, and a hydrophobic portion, which is a long chain hydrocarbon moiety, such as an alkyl. In the anionic surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0535] Nonionic surfactants typically contain no charged groups and have a hydrophobic portion that is a long hydrocarbon chain. The hydrophilic portion of the nonionic surfactant contains water-soluble functional groups, such as ethylene ether chains derived from polymerization with ethylene oxide. In the nonionic surfactant, the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0536] Examples of nonionic surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

[0537] Specific examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene behenyl ether.

[0538] Specific examples of polyoxyethylene alkylphenyl ethers include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0539] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.

[0540] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0541] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0542] Specific examples of glycerol esters include glycerol monomyristate, glycerol monostearate, and glycerol monooleate.

[0543] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

[0544] The ethers and esters may have an HLB value of 10-18.

[0545] Examples of nonionic surfactants include the 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.), and Tergitol (registered trademark) L series, all manufactured by Dow Chemical Company; the Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m to 22, n to 23)), and the Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10).

[0546] Examples of anionic hydrocarbon surfactants include Versatic (registered trademark) 10 manufactured by Resolution Performance Products, and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0547] Other compounds having surface activity include RLM (wherein R is a linear or branched alkyl group having one or more carbon atoms which may have a substituent, or a cyclic alkyl group having three or more carbon atoms which may have a substituent, and when the number of carbon atoms is three or more, it may contain a monovalent or divalent heterocycle or may form a ring). L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or NR5 4(R 5 may be the same or different and are H or an organic group (preferably an organic group not containing fluorine), an imidazolium group which may have a substituent, a pyridinium group which may have a substituent, or a phosphonium group which may have a substituent. - is an aryl sulfonate. ) 5 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, CH3-(CH2) such as lauric acid n -LM (wherein n is an integer of 6 to 17, and L and M are the same as above). Mixtures in which R is an alkyl group having 12 to 16 carbon atoms and LM is sulfate or sodium dodecyl sulfate (SDS) can also be used. Other surfactant compounds include R 6 (-LM)2(wherein, R 6 is a linear or branched alkylene group having one or more carbon atoms which may have a substituent, or a cyclic alkylene group having three or more carbon atoms which may have a substituent, and when the number of carbon atoms is three or more, it may contain a monovalent or divalent heterocycle or may form a ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or 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 aryl sulfonate. ) Other surfactant compounds include R 7 (-LM)3(wherein, R 7is a linear or branched alkylidyne group having one or more carbon atoms which may have a substituent, or a cyclic alkylidyne group having three or more carbon atoms which may have a substituent, and when the number of carbon atoms is three or more, it may contain a monovalent or divalent heterocycle or may form a ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or 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 that does not contain fluorine). - is an aryl sulfonate. )

[0548] Siloxane hydrocarbon surfactants include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of the siloxane surfactant comprises a distinct hydrophobic portion and a hydrophilic portion. The hydrophobic portion comprises one or more dihydrocarbylsiloxane units, where the substituents on the silicone atom are entirely hydrocarbon. These siloxane surfactants can also be considered hydrocarbon surfactants in the sense that the carbon atoms of the hydrocarbyl groups are fully substituted by hydrogen atoms, which may be substituted by halogens such as fluorine, i.e., the monovalent substituents on the carbon atoms of the hydrocarbyl groups are hydrogen. In the above siloxane surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0549] Siloxane hydrocarbon surfactants are also disclosed in US Pat. No. 6,841,616.

[0550] Siloxane-based anionic hydrocarbon surfactants include SilSense available from Noveon® Consumer Specialties, manufactured by Lubrizol Advanced Materials, Inc. TM PE-100 Silicone, SilSense TM CA-1 silicone and the like.

[0551] Examples of anionic hydrocarbon surfactants include the sulfosuccinate surfactant Lankropol (registered trademark) K8300 manufactured by Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate surfactants include sodium diisodecyl sulfosuccinate (Emulsogen (registered trademark) SB10 manufactured by Clariant) and sodium diisotridecyl sulfosuccinate (Polirol (registered trademark) TR / LNA manufactured by Cesapinia Chemicals).

[0552] Other surfactant compounds include PolyFox (registered trademark) surfactants manufactured by Omnova Solutions, Inc. TM PF-156A, PolyFox TM PF-136A, etc.)

[0553] The other surfactant compound is preferably an anionic hydrocarbon surfactant. As the anionic hydrocarbon surfactant, those described above can be used, but for example, the following hydrocarbon surfactants can be suitably used.

[0554] Examples of the anionic hydrocarbon surfactant include those represented by the following formula (α): R 100 -COOM (α) (In the formula, R 100is 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, wherein R 101 R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 101 The organic group in R is preferably an alkyl group. 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant activity, R 100 The number of carbon atoms in R is preferably 2 or more, and more preferably 3 or more. 100 The number of carbon atoms is preferably 29 or less, and more preferably 23 or less. The metal atom of M includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K, or Li. M may be 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 even more preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0555] The compound (α) includes R 102 -COOM(in the formula, 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 number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above.) Specifically, CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28, and M is the same as above).

[0556] From the viewpoint of emulsion stability, the compound (α) may not contain a carbonyl group (excluding a carbonyl group in a carboxyl group). Examples of the hydrocarbon-containing surfactant that does not contain a carbonyl group include surfactants represented by the following formula (A1): R 103 -COO-M (A1) (In the formula, R 103 is an alkyl group, an alkenyl group, an alkylene group, or an alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond; M is H, a metal atom, NR 101 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 101 are the same or different and each represents H or an organic group (preferably an organic group not containing fluorine). In the above formula (A1), R 103 is preferably an alkyl group or an alkenyl group (which may contain an ether group). 103 The alkyl group or alkenyl group in the above R may be linear or branched. 103 The number of carbon atoms is not limited, but is, for example, 2 to 29.

[0557] When the alkyl group is linear, R 103 The number of carbon atoms in R is preferably 3 to 29, and more preferably 5 to 23. When the alkyl group is branched, R 103 The number of carbon atoms is preferably 5 to 35, and more preferably 11 to 23. When the alkenyl group is linear, R 103 The number of carbon atoms in R is preferably 2 to 29, and more preferably 9 to 23. When the alkenyl group is branched, R 103The number of carbon atoms is preferably 2 to 29, and more preferably 9 to 23.

[0558] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, and a vinyl group.

[0559] Examples of the 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, croscarmellose ... Examples of suitable oleic acids include oleic 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, osbondo acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, herring 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 preferred. The salts include those in which the hydrogen of the carboxyl group is replaced by a metal atom of the formula M, NR 11 4. Examples include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent.

[0560] The anionic hydrocarbon surfactant also includes, for example, a surfactant represented by 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, wherein R 101 R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. 101 The organic group in R is preferably an alkyl group. 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant activity, R 100 The number of carbon atoms in R is preferably 2 or more, and more preferably 3 or more. 100 The number of carbon atoms is preferably 29 or less, and more preferably 23 or less. The metal atom of M includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K, or Li. M may be 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 even more preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0561] The compound (β) includes R 102 -SO3M (in the formula, R 102is 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 number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above.) Specifically, CH3-(CH2) n -SO3M (wherein n is an integer of 2 to 28, and M is the same as above) are exemplified.

[0562] From the viewpoint of emulsion stability, the compound (β) may not contain a carbonyl group (excluding a carbonyl group in a carboxyl group). Examples of the hydrocarbon-containing surfactant that does not contain a carbonyl group include surfactants represented by the following formula (B1): R 103 -SO3-M (B1) (In the formula, R 103 is an alkyl group, an alkenyl group, an alkylene group, or an alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond; M is H, a metal atom, NR 101 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 101 are the same or different and each represents H or an organic group (preferably an organic group not containing fluorine). In the above formula (B), R 103 is preferably an alkyl group or an alkenyl group (which may contain an ether group). 103 The alkyl group or alkenyl group in the above R may be linear or branched. 103 The number of carbon atoms is not limited, but is, for example, 2 to 29.

[0563] When the alkyl group is linear, R 103The number of carbon atoms in R103 is preferably 3 to 29, and more preferably 5 to 23. When the alkyl group is branched, the number of carbon atoms in R103 is preferably 5 to 35, and more preferably 11 to 23. When the alkenyl group is linear, R 103 The number of carbon atoms in R103 is preferably 2 to 29, and more preferably 9 to 23. When the alkenyl group is branched, the number of carbon atoms in R103 is preferably 2 to 29, and more preferably 9 to 23.

[0564] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, and a vinyl group.

[0565] Examples of the compound (β) include aliphatic, unsaturated aliphatic, and aromatic sulfonic acids, aliphatic, unsaturated aliphatic, and aromatic sulfates, and salts thereof. Examples of the sulfonic acids include 1-hexanesulfonic acid, 1-octane sulfonic 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, and butylnaphthalenesulfonic acid. Examples of the sulfates include sodium alkyl sulfates, alpha-sulfofatty acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alpha-olefin sulfonates, lauryl sulfate, myristyl sulfate, laureth sulfate, and polyoxyethylene alkylphenol sulfonic acid. As the compound (β), at least one selected from the group consisting of saturated aliphatic and aromatic sulfate esters and their salts is particularly preferred, and at least one selected from the group consisting of sodium alkyl sulfate esters, alpha-sulfofatty acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alpha-olefin sulfonates, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid, and their salts is more preferred. The salts include those in which the hydrogen of the sulfonic acid group is replaced by a metal atom of the above formula M, NR 11 4. Examples include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent.

[0566] The anionic hydrocarbon surfactant may be a surfactant represented by the following formula (1-0A): [ka] (In the formula, R 1A ~R 5A represents H, a monovalent hydrocarbon group which may contain an ester group between carbon atoms, or a group represented by the general formula: -X A -A, where R 2A and R 5A At least one of the groups has the general formula: -X A - represents a group represented by A. X A is, in each occurrence, the same or different, a divalent hydrocarbon radical or a bond; A is the same or different in each occurrence and is -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 a fluorine-free organic group); R 1A ~R 5AAny two of these may be bonded to each other to form a ring.

[0567] In general formula (1-0A), R 1A ~R 5A In R, the monovalent hydrocarbon group which may contain an ester group between carbon atoms preferably has 1 to 50 carbon atoms, more preferably 5 to 20 carbon atoms. 1A ~R 5A Any two of these may be bonded to each other to form a ring. The monovalent hydrocarbon group which may contain an ester group between carbon atoms is preferably an alkyl group. In the formula, X A In the formula, the number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 50, and more preferably 5 to 20. Examples of the divalent hydrocarbon group include an alkylene group and an alkanediyl group, with an alkylene group being preferred.

[0568] In general formula (1-0A), R 2A and R 5A any one of the above general formula: -X A -A is preferred, and R 2A is represented by the above general formula: -X A A group represented by -A is more preferred.

[0569] In the general formula (1-0A), a preferred embodiment is R 2A is represented by the general formula: -X A -A, and R 1A , R 3A , R 4A and R 5A is H. In this case, X A is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0570] In the general formula (1-0A), a preferred embodiment is also R 2A is represented by the general formula: -X A -A, and R 1A and R 3A Ga-YA -R 6 and Y A is the same or different in each occurrence and is -COO-, -OCO-, or a bond; R 6 are the same or different in each occurrence and are alkyl groups having 2 or more carbon atoms. In this case, R 4A and R 5A is preferably H.

[0571] Examples of hydrocarbon surfactants represented by general formula (1-0A) include glutaric acid or a salt thereof, adipic acid or a salt thereof, pimelic acid or a salt thereof, suberic acid or a salt thereof, azelaic acid or a salt thereof, and sebacic acid or a salt thereof. Furthermore, the aliphatic carboxylic acid hydrocarbon surfactant represented by general formula (1-0A) may be a two-chain two-hydrophilic group synthetic surfactant, and examples of such Gemini surfactants include Geminisurf (Chukyo Yushi Co., Ltd.), Gemsurf α142 (12 carbon atoms, lauryl group), Gemsurf α102 (10 carbon atoms), and Gemsurf α182 (14 carbon atoms).

[0572] The anionic hydrocarbon surfactant may be a surfactant represented by the following formula I: R-(XZ) n (I) (wherein R is a hydrophobic hydrocarbon moiety containing one or more saturated or unsaturated, acyclic or cyclic aliphatic groups; the percentage of the total of CH groups relative to the total of CH, CH, and CH groups in the one or more aliphatic groups is at least about 70%, and the hydrophobic moiety does not contain a siloxane unit; each X, which may be the same or different, represents an ionic hydrophilic moiety; each Z, which may be the same or different, represents one or more counter ions of the ionic hydrophilic moiety; and n is 1 to 3.)

[0573] Compound I exhibits low reactivity with the polymerization initiator and / or propagating fluoropolymer radical in the emulsion polymerization of fluoromonomers.

[0574] Compound I has the formula: [ka] (In the formula, Y + is hydrogen, ammonium, quaternary ammonium, a nitrogen heterocycle, an alkali metal, or an alkaline earth metal.

[0575] Compound I has the following formula II: [ka] (In the formula, R 2’ and R 2’’’ are the same or different and are saturated or unsaturated, acyclic or cyclic aliphatic groups having 4 to 16 carbon atoms; R 2’ and R 2’’’ the percentage of the total of CH3 groups to the total of CH3, CH2 and CH groups in the group is at least about 70%, or 2’ and R 2’’’ may be linked together to form a saturated or unsaturated aliphatic ring which may contain ether or ester linkages, provided that the percentage of the total of CH3 groups relative to the total of CH3, CH2, and CH groups in the ring is at least about 70%. 1 is hydrogen, methoxy, ethoxy or phenoxy. + is hydrogen, ammonium, quaternary ammonium, a nitrogen heterocycle, an alkali metal, or an alkaline earth metal.

[0576] As compound II, for example, the following compounds are preferred. [ka] Y in the above formula + may be hydrogen, ammonium, or an alkali metal.

[0577] Compound I has the following formula III: [ka] (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; R 3 , R 4’ , and R 4’’ The percentage of total CH3 with respect to the total of CH3, CH2 and CH groups in the group is at least about 70%, provided that R 3 , R 4’ , and R 4’’ At least one of the groups is not hydrogen, and R 4’ and R 4’’ is hydrogen, R 3 is not hydrogen, but R 3 is hydrogen, R 4’ and R 4’’ is not hydrogen. Y + is hydrogen, ammonium, quaternary ammonium, a nitrogen heterocycle, an alkali metal, or an alkaline earth metal.

[0578] As the compound III, for example, the following compounds are preferred. [ka] Y in the above formula + may be hydrogen, ammonium, or an alkali metal.

[0579] The TFE polymer composition of the present disclosure can be obtained, even in the case where the above-mentioned specific hydrocarbon surfactant is not used, by a production method including a polymerization step of polymerizing tetrafluoroethylene alone or tetrafluoroethylene and the above-mentioned modified monomer copolymerizable with tetrafluoroethylene in an aqueous medium having a pH of 4.0 or higher in the presence of a hydrocarbon surfactant and a polymerization initiator to obtain a TFE polymer. Conventionally, an acidic polymerization initiator has been used in the polymerization process for producing a TFE-based polymer, and therefore the pH of the aqueous medium used in the polymerization has been less than 4.0. As a result of intensive studies by the present inventors, it has been unexpectedly found that the stability of the polymerization can be improved by adjusting the pH of the aqueous medium used in the polymerization to 4.0 or more, and a TFE-based polymer with a high molecular weight can be produced. In the above production method, tetrafluoroethylene alone, or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene, are polymerized in an aqueous medium having a pH of 4.0 or higher. The pH may be 4.0 or higher, preferably greater than 4.0, more preferably 4.5 or higher, even more preferably 5.0 or higher, even more preferably 5.5 or higher, especially preferably 6.0 or higher, particularly 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, but may be, for example, 13.0 or lower. From the viewpoint of corrosion of the polymerization vessel, it is preferably 12.0 or lower, more preferably 11.5 or lower, and even more preferably 11.0 or lower. The pH can be measured using a pH meter.

[0580] In the above-mentioned production method, the method for adjusting the pH of the aqueous medium to 4.0 or higher is not particularly limited. For example, the pH can be adjusted to 4.0 or higher by using an alkaline aqueous solution, an alkaline aqueous dispersion, or a pH adjuster, but is not particularly limited thereto. Even when a polymerization initiator that is acidic when dissolved in an aqueous medium is used, the pH can be adjusted to 4.0 or higher by further adding an alkaline compound such as sodium hydroxide. - Any compound capable of generating the above may be used, and examples thereof include, but are not limited to, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc. The polymerization step may include a step of adding an alkali compound to the aqueous medium.

[0581] In the above production method, the pH of the aqueous medium may be 4.0 or higher throughout the entire polymerization step. Alternatively, the pH may be 4.0 or higher in the middle of the polymerization step, or in the latter half of the polymerization step. Alternatively, the pH may be 4.0 or higher in both the middle and latter half of the polymerization step.

[0582] In the polymerization step, it is preferable that the pH of the aqueous medium is 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, especially preferably 99% or more, especially preferably 100%) of the period from the start of polymerization to the point where the polymer solids concentration reaches 3% by mass (preferably 5% by mass, more preferably 8% by mass, even more preferably 10% by mass, even more preferably 15% by mass, especially more preferably 18% by mass, especially more preferably 20% by mass, especially preferably 25% by mass). In the polymerization step, it is preferable that the pH of the aqueous medium is 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, especially preferably 99% or more, and particularly preferably 100%) of the period from when the polymer solids concentration reaches 10% by mass (preferably 8% by mass, more preferably 5% by mass, even more preferably 3% by mass, and even more preferably from the start of polymerization) to when the polymer solids concentration reaches 15% by mass. In the polymerization step, it is preferable that the pH of the aqueous medium is 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, especially preferably 99% or more, and particularly preferably 100%) of the period from when the polymer solids concentration is 15% by mass to when the polymer solids concentration is 18% by mass (preferably 20% by mass, more preferably 25% by mass). In the polymerization step, it is preferable that the pH of the aqueous medium is 4.0 or higher for a period of 60% or more (preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, more preferably 99% or more, especially preferably 100%) from the time when the polymer solids concentration reaches 25% by mass (preferably 20% by mass, more preferably 18% by mass, even more preferably 15% by mass, even more preferably 10% by mass, especially more preferably 8% by mass, particularly preferably 5% by mass, more preferably 3% by mass, and even more preferably the start of polymerization) to the time when the polymerization is completed. In any case, the pH of the aqueous medium is preferably greater than 4.0, more preferably 4.5 or higher, even more preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, particularly preferably 6.5 or higher, more preferably 7.0 or higher, even more preferably 7.5 or higher, and even more preferably 8.0 or higher.

[0583] In the above-mentioned production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, more preferably a carboxylic acid hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid hydrocarbon surfactant are not particularly limited, but for example, the compound (α) exemplified among the above-mentioned other compounds having surface activity can be suitably used.

[0584] In the above-mentioned production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and also preferably a sulfonic acid hydrocarbon surfactant. The anionic hydrocarbon surfactant and the sulfonic acid hydrocarbon surfactant are not particularly limited. For example, the compound (β) exemplified among the above-mentioned other compounds having surface activity can be suitably used.

[0585] Even if the TFE polymer composition of the present disclosure does not use the above-mentioned specific hydrocarbon surfactant, it comprises the polymerization step of obtaining a TFE polymer by polymerizing tetrafluoroethylene alone or tetrafluoroethylene and the modified monomer copolymerizable with the above-mentioned tetrafluoroethylene in an aqueous medium in the presence of anionic hydrocarbon surfactant and a polymerization initiator, and the above-mentioned hydrocarbon surfactant comprises the salt of the hydrocarbon surfactant.In other words, at least a part of the anionic hydrocarbon surfactant in the above-mentioned polymerization step is in the form of a salt. As a result of intensive studies, the present inventors have unexpectedly found that when an anionic hydrocarbon surfactant contains a salt of the anionic hydrocarbon surfactant, the stability of polymerization is improved and a TFE polymer having a large molecular weight can be produced. The anionic hydrocarbon surfactants will be described later. Whether the anionic hydrocarbon surfactant contains a salt of the hydrocarbon surfactant can be confirmed by measuring the electrical conductivity. In the above-mentioned production method, the concentration of the salt of the anionic hydrocarbon surfactant is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of the anionic hydrocarbon surfactant. The proportion of the salt can be measured by the solution concentration and conductivity. In the above-mentioned production method, the hydrocarbon surfactant is preferably a carboxylic acid-type hydrocarbon surfactant, and the hydrocarbon surfactant does not contain fluorine. In the salts of anionic hydrocarbon surfactants, the cations (excluding hydrogen atoms) that replace the hydrogen atoms of the acid are, for example, metal atoms, NR y 4(R ymay be the same or different and each represents H or an organic group (preferably an organic group not containing fluorine), an imidazolium group which may have a substituent, a pyridinium group which may have a substituent, or a phosphonium group which may have a substituent. y is preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. The cation in the salt of the anionic hydrocarbon surfactant may be a metal atom or NR y 4 is preferred, NR y 4 is more preferred, and NH4 is even more preferred. Since conductivity is greatly affected by temperature, a thermostatic bath is used to keep the sample liquid temperature at 25°C, and the pH meter cell temperature is also kept at the same level before measuring the conductivity.

[0586] In the above-mentioned production method, the polymerization step is preferably carried out substantially in the absence of the hydrocarbon surfactant in the form of an organic acid. By carrying out the polymerization substantially in the absence of the hydrocarbon surfactant in the form of an organic acid, the stability of the polymerization is further improved, and a high molecular weight TFE polymer can be obtained. Substantially in the absence of the hydrocarbon surfactant in the form of an organic acid means that the concentration of the organic acid is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, particularly preferably 0.05 mass% or less, and particularly preferably 0.01 mass% or less, relative to the mass of the obtained aqueous dispersion. In this specification, the term "organic acid" refers to an organic compound that exhibits acidity. Examples of organic acids include carboxylic acids having a -COOH group and sulfonic acids having a -SOH group. Carboxylic acids are preferred because they allow for easy adjustment of the pH of an aqueous solution containing the organic acid. Furthermore, the "form of organic acid" refers to a form in which the H of the acidic group (for example, -COOH group, -SO3H group, etc.) contained in the organic acid is not free. In the above production method, the hydrocarbon surfactant is an anionic hydrocarbon surfactant.

[0587] In the polymerization step, the amount of hydrocarbon surfactant at the start of polymerization is preferably more than 50 ppm relative to the aqueous medium. The amount of hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or more, more preferably 70 ppm or more, even more preferably 80 ppm or more, and even more preferably 100 ppm or more. There is no particular upper limit, but for example, it is preferably 10,000 ppm, and more preferably 5,000 ppm. By keeping the amount of hydrocarbon surfactant at the start of polymerization within the above range, an aqueous dispersion having a smaller average primary particle size and better stability can be obtained. Polymerization can be said to have begun when the gaseous TFE in the reactor becomes a TFE-based polymer and a pressure drop occurs in the reactor. U.S. Pat. No. 3,391,099 (Punderson) discloses dispersion polymerization of tetrafluoroethylene in an aqueous medium, which consists of two distinct stages in the polymerization process: first, the formation of polymer nuclei as nucleation sites, and then, a growth stage involving the polymerization of the established particles. Polymerization usually begins when both the monomer to be polymerized and the polymerization initiator are charged into the reactor. In this disclosure, the additive involved in the formation of nucleation sites is referred to as a nucleating agent.

[0588] The polymerization step preferably includes an addition step of adding a composition containing a hydrocarbon surfactant after the initiation of polymerization, which further improves the stability of the polymerization and allows a TFE polymer with a higher molecular weight to be obtained. The hydrocarbon surfactant may be in the form of, for example, a solid (for example, a powder of a hydrocarbon surfactant) or a liquid. The composition may be any composition containing a hydrocarbon surfactant, and may consist of only a hydrocarbon surfactant, or may be a solution or dispersion of a hydrocarbon surfactant containing a hydrocarbon surfactant and a liquid medium. Therefore, the addition step can also be said to be a step of adding a hydrocarbon surfactant alone or a composition containing a hydrocarbon surfactant after the initiation of polymerization. The hydrocarbon surfactant is not limited to one type, and may be a mixture of two or more types. The liquid medium may be either an aqueous medium or an organic solvent, or a combination of an aqueous medium and an organic solvent may be used. Specific examples of the composition include an aqueous solution in which a hydrocarbon surfactant is dissolved in an aqueous medium, and an aqueous dispersion in which a hydrocarbon surfactant is dispersed in an aqueous medium.

[0589] The amount of the hydrocarbon surfactant added in the addition step is preferably 0.0001 to 10% by mass relative to the aqueous medium. It is more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more, relative to the aqueous medium. It is also more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less, relative to the aqueous medium.

[0590] The composition is preferably an aqueous solution containing a hydrocarbon surfactant and having a pH of 5.0 or higher, since this improves the stability of the polymerization and allows a TFE polymer with a higher molecular weight to be obtained. The pH of the aqueous solution is preferably 6.0 or higher, more preferably 6.5 or higher, even more 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, but may be 12.0 or lower, or may be 11.0 or lower.

[0591] The hydrocarbon surfactant used in the above-mentioned addition step is preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid type hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid type hydrocarbon surfactant are not particularly limited, but for example, the compound (α) exemplified among the above-mentioned other compounds having surface activity can be suitably used.

[0592] The carboxylic acid type hydrocarbon surfactant used in the polymerization step and the addition step includes the surfactant (e) and surfactants represented by the above formula: R 6 (-LM)2 and anionic surfactants represented by the above formula: R 7 Among the anionic surfactants represented by (-LM)3, at least one selected from the group consisting of those having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.), the above compound (α), the above surfactant (1-0A), and surfactants obtained by radical treatment or oxidation treatment of these surfactants is preferred. The above carboxylic acid type hydrocarbon surfactants may be used alone or as a mixture of two or more types. The compound (α) has the above-mentioned formula: R 102 -COOM(in the formula, R 102 and M are the same as above.), as well as anionic surfactants represented by the above formula: RLM (wherein R, L, and M are the same as above), and surfactants (c) and (d) above which have a carboxyl group (—COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.).

[0593] The carboxylic acid type hydrocarbon surfactant is preferably the compound (α), and is preferably a compound represented by the formula (A1), a compound represented by the formula (c), c Ga-COOX c A compound represented by the formula (d) d Ga-COOX d A compound represented by the formula (e) e -COOM eand a compound represented by the above formula (1-0A) in which A is -COOM, and a compound obtained by subjecting these compounds to radical treatment or oxidation treatment, and further preferably at least one selected from the group consisting of a compound represented by the above formula (A1) and a compound obtained by subjecting these compounds to radical treatment or oxidation treatment. Particularly preferred is at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, salts thereof, and compounds obtained by radical treatment or oxidation treatment of these compounds. As the salts, those in which the hydrogen of the carboxyl group is bonded to a metal atom of the above-mentioned formula M, NR 101 4. Examples include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent.

[0594] The above production method preferably involves polymerizing tetrafluoroethylene substantially in the absence of a fluorine-containing surfactant. In the above production method, "substantially in the absence of a fluorinated surfactant" means that the fluorinated surfactant is present at 10 ppm by mass or less relative to the aqueous medium, preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably 10 ppb by mass or less, still more preferably less than 10 ppb by mass, still more preferably 1 ppb by mass or less, and particularly preferably less than 1 ppb by mass. "Substantially in the absence of a fluorine-containing surfactant" also means that no fluorine-containing surfactant is intentionally added.

[0595] The fluorine-containing surfactant may, for example, be an anionic fluorine-containing surfactant. The anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less excluding the anionic group.

[0596] The fluorine-containing surfactant may also be a surfactant containing fluorine in the anionic moiety having a molecular weight of 1,000 or less, preferably 800 or less. The "anionic portion" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF2) represented by the formula (I) below n1 In the case of COOM, "F(CF2) n1 The "COO" part.

[0597] Specific examples of the fluorine-containing surfactants include those described in U.S. Patent Application Publication Nos. 2007 / 0015864, 2007 / 0015865, 2007 / 0015866, 2007 / 0276103, 2007 / 0117914, 2007 / 142541, 2008 / 0015319, and U.S. Pat. No. 3,250,808. , U.S. Pat. No. 3,271,341, JP 2003-119204 A, WO 2005 / 042593, WO 2008 / 060461, WO 2007 / 046377, WO 2007 / 119526, WO 2007 / 046482, WO 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, WO 2013 / 189824, and WO 2013 / 189826.

[0598] The anionic fluorine-containing surfactants include those represented by the above-mentioned general formula (N 0 ) is an example of a compound represented by the formula:

[0599] As described above, examples of the anionic fluorine-containing surfactant include carboxylic acid-based fluorine-containing surfactants and sulfonic acid-based fluorine-containing surfactants.

[0600] The TFE polymer composition of the present disclosure can be suitably produced by a production method including an addition step of adding at least one selected from the group consisting of a radical scavenger and a decomposer of a polymerization initiator. The addition step is carried out during the above-mentioned emulsion polymerization step in an aqueous medium. The radical concentration during polymerization can be adjusted by adding a radical scavenger or a decomposer of a polymerization initiator. From the viewpoint of reducing the radical concentration, a radical scavenger is preferred.

[0601] The radical scavenger is a compound that does not have the ability to restart after addition or chain transfer to a free radical in the polymerization system. Specifically, a compound that easily undergoes a chain transfer reaction with a primary radical or a propagating radical to generate a stable radical that does not subsequently react with the monomer, or a compound that easily undergoes an addition reaction with a primary radical or a propagating radical to generate a stable radical, is used. Generally, the activity of what is called a chain transfer agent is characterized by the chain transfer constant and the reinitiation efficiency, but among chain transfer agents, those with a reinitiation efficiency of almost 0% are called radical scavengers. The radical scavenger can also be described as a compound whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant and whose reinitiation efficiency is substantially zero percent. "Reinitiation efficiency is substantially zero percent" means that the generated radicals turn the radical scavenger into stable radicals. Preferably, the compound has a chain transfer constant (Cs) with TFE at the polymerization temperature (=chain transfer rate constant (kc) / polymerization rate constant (kp)) of more than 0.1, and the compound has a chain transfer constant (Cs) of more preferably 0.5 or more, even more preferably 1.0 or more, even more preferably 5.0 or more, and particularly preferably 10 or more.

[0602] The radical scavenger in the present disclosure is preferably at least one selected from the group consisting of, for example, aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl). Examples of aromatic hydroxy compounds include unsubstituted phenol, polyhydric phenol, salicylic acid, m- or p-salicylic acid, gallic acid, and naphthol. Examples of the unsubstituted phenol include o-, m-, or p-nitrophenol, o-, m-, or p-aminophenol, p-nitrosophenol, etc. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, naphthresorcinol, etc. Examples of aromatic amines include o-, m-, or p-phenylenediamine, benzidine, and the like. Examples of the quinone compound include o-, m-, or p-benzoquinone, 1,4-naphthoquinone, and alizarin. Examples of thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN). Of the above radical scavengers, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

[0603] The amount of radical scavenger added is preferably an amount equivalent to 3 to 500% (molar basis) of the polymerization initiator concentration, from the viewpoint of reducing the standard specific gravity. A more preferred lower limit is 5% (molar basis), even more preferably 8% (molar basis), even more preferably 10% (molar basis), even more preferably 15% (molar basis), especially preferably 20% (molar basis), particularly preferably 25% (molar basis), especially preferably 30% (molar basis), especially preferably 35% (molar basis). A more preferred upper limit is 400% (molar basis), even more preferably 300% (molar basis), even more preferably 200% (molar basis), especially preferably 100% (molar basis).

[0604] The polymerization initiator decomposer may be any compound capable of decomposing the polymerization initiator used, and is preferably at least one selected from the group consisting of sulfites, bisulfites, bromates, diimines, diimine salts, oxalic acid, oxalates, copper salts, and iron salts. Examples of sulfites include sodium sulfite and ammonium sulfite. Examples of copper salts include copper(II) sulfate, and examples of iron salts include iron(II) sulfate. The amount of the polymerization initiator decomposer added is in the range of 25 to 300% by mass, preferably 25 to 150% by mass, and more preferably 50 to 100% by mass, based on the amount of the oxidizing agent combined as the polymerization initiator (redox initiator described below). The amount of decomposer for the polymerization initiator added is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration, from the viewpoint of reducing the standard specific gravity. A more preferred lower limit is 5% (molar basis), even more preferably 8% (molar basis), even more preferably 10% (molar basis), even more preferably 13% (molar basis), and even more preferably 15% (molar basis). A more preferred upper limit is 400% (molar basis), even more preferably 300% (molar basis), even more preferably 200% (molar basis), and especially preferably 100% (molar basis).

[0605] At least one selected from the group consisting of a radical scavenger and a decomposer of a polymerization initiator is preferably added when the concentration of the TFE polymer formed in the aqueous medium is 5% by mass or more, more preferably 10% by mass or more. It is also preferable to add the TFE polymer when the concentration of the TFE polymer formed in the aqueous medium is 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0606] The adding step may be a step of continuously adding at least one selected from the group consisting of a radical scavenger and a decomposer for a polymerization initiator. Continuously adding at least one selected from the group consisting of radical scavengers and decomposers for polymerization initiators means, for example, adding at least one selected from the group consisting of radical scavengers and decomposers for polymerization initiators over time, without interruption, or in portions, rather than all at once.

[0607] The polymerization step may further comprise polymerizing tetrafluoroethylene in the presence of a nucleating agent.

[0608] The nucleating agent is preferably at least one selected from the group consisting of, for example, fluoropolyethers, nonionic surfactants, and chain transfer agents. In this case, the polymerization step is preferably a step of obtaining a TFE-based polymer by polymerizing tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon surfactant and the nucleating agent.

[0609] The fluoropolyether is preferably a perfluoropolyether.

[0610] The above fluoropolyether preferably has repeating units represented by formulas (1a) to (1d). (-CFCF3-CF2-O-) n (1a) (-CF2-CF2-CF2-O-) n (1b) (-CF2-CF2-O-) n -(-CF2-O-) m (1c) (-CF2-CFCF3-O-) n -(-CF2-O-) m (1d) (In formulas (1a) to (1d), m and n are integers of 1 or more.)

[0611] The fluoropolyether is preferably a fluoropolyether acid or its salt, and the fluoropolyether acid is preferably a carboxylic acid, a sulfonic acid, a sulfonamide, or a phosphonic acid, and more preferably a carboxylic acid. Among the fluoropolyether acids or their salts, the salt of a fluoropolyether acid is preferred, the ammonium salt of a fluoropolyether acid is more preferred, and the ammonium salt of a fluoropolyether carboxylic acid is even more preferred.

[0612] The fluoropolyether acids or salts thereof can have any 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. Two or more types of fluorocarbon groups can be present in the molecule.

[0613] The fluoropolyether acid or salt thereof is selected from the group consisting of fluoropolyether acids and fluoropolyether salts having the following formula: CF3-CF2-CF2-O(-CFCF3-CF2-O-) n CFCF3-COOH, CF3-CF2-CF2-O(-CF2-CF2-CF2-O-) n -CF2-CF2COOH, or HOOC-CF2-O(-CF2-CF2-O-) n -(-CF2-O-) m CF2COOH (wherein m and n are the same as above.) or a salt thereof.

[0614] These structures are discussed by Kasai in J. Appl. Polymer Sci., 57, 797 (1995). As disclosed therein, such fluoropolyethers can have carboxylic acid groups or salts thereof at one or both ends. Similarly, such fluoropolyethers can have sulfonic or phosphonic acid groups or salts thereof at one or both ends. In addition, fluoropolyethers with acid functional groups at both ends can have different groups at each end. For monofunctional fluoropolyethers, the other end of the molecule is usually perfluorinated, but may contain hydrogen or chlorine atoms.

[0615] Fluoropolyethers having acid groups at one or both ends have at least two ether oxygens, preferably at least four ether oxygens, and 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 2 or 3 carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. Also, preferably, the fluoropolyether has a total of at least 15 carbon atoms, and for example, the preferred minimum value of n or n + m in the above repeating unit structure is at least 5. Two or more fluoropolyethers having acid groups at one or both ends can be used in the method according to the present disclosure. Typically, unless special care is taken in the preparation of a single specific fluoropolyether compound, the fluoropolyether may contain multiple compounds in various proportions within the molecular weight range relative to the average molecular weight.

[0616] The fluoropolyether preferably has a number average molecular weight of 800 g / mol or more. Because the fluoropolyether acid or its salt may be difficult to disperse in an aqueous medium, the number average molecular weight is preferably less than 6000 g / mol. The fluoropolyether acid or its salt more preferably has a number average molecular weight of 800 to 3500 g / mol, and even more preferably 1000 to 2500 g / mol.

[0617] The amount of the fluoropolyether is preferably 5 to 3000 ppm, more preferably 5 to 2000 ppm, with a more preferred lower limit of 10 ppm and a more preferred upper limit of 100 ppm relative to the aqueous medium.

[0618] The nonionic surfactant as the nucleating agent may be any of the nonionic surfactants described above, and is preferably a nonionic surfactant that does not contain fluorine. For example, the nonionic surfactant may be a nonionic surfactant represented by the following general formula (i): R 3 -OA 1 -H(i) (In the formula, R 3 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain. R 3 The number of carbon atoms in R is preferably 10 to 16, and more preferably 12 to 16. 3 When the carbon number of R is 18 or less, good dispersion stability of the aqueous dispersion is easily obtained. 3 If the carbon number exceeds 18, the flow temperature is high and it is difficult to handle. 3 If the number of carbon atoms is less than 8, the surface tension of the aqueous dispersion increases, and the permeability and wettability tend to decrease.

[0619] The polyoxyalkylene chain may be composed of oxyethylene and oxypropylene. The polyoxyalkylene chain has an average repeat number of 5 to 20 oxyethylene groups and an average repeat number of 0 to 2 oxypropylene groups, and is a hydrophilic group. The number of oxyethylene units may include either a broad or narrow unimodal distribution, which is typically provided, or a broader or bimodal distribution obtained by blending. When the average repeat number of oxypropylene groups is greater than 0, the oxyethylene and oxypropylene groups in the polyoxyalkylene chain may be arranged in a block or random configuration. From the viewpoint of viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain having an average repeat number of 7 to 12 oxyethylene groups and an average repeat number of 0 to 2 oxypropylene groups is preferred. 1 If the oxypropylene group has an average of 0.5 to 1.5, low foaming properties are favorable and it is preferable.

[0620] More preferably, R 3 is (R')(R")HC-, where R' and R" are the same or different straight, branched, or cyclic alkyl groups having a total of at least 5, preferably 7 to 17, carbon atoms. Preferably, at least one of R' or R" is a branched or cyclic hydrocarbon group.

[0621] Specific examples of the polyoxyethylene alkyl ether include C 13 H 27 -O-(C2H4O) 10 -H, C 12 H 25 -O-(C2H4O) 10 -H, C 10 H 21 CH(CH3)CH2-O-(C2H4O)9-H, C 13 H 27 -O-(C2H4O)9-(CH(CH3)CH2O)-H, C 16 H 33 -O-(C2H4O) 10 -H, HC(CH 11 )(C7H 15)-O-(C2H4O)9-H, etc. Examples of commercially available polyoxyethylene alkyl ethers include Genapol X080 (product name, manufactured by Clariant), the Noigen TDS series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) such as Noigen TDS-80 (trade name), the Leocol TD series (manufactured by Lion Chemical) such as Leocol TD-90 (trade name), the Lionol (registered trademark) TD series (manufactured by Lion Chemical), the T-Det A series (manufactured by Harcros Chemicals) such as T-Det A138 (trade name), and the Tergitol (registered trademark) 15S series (manufactured by Dow Chemical).

[0622] The nonionic surfactant is preferably an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 4 to about 18 ethylene oxide units, an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 6 to about 12 ethylene oxide units, or a mixture thereof. Nonionic surfactants of this type are also commercially available, for example, as TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (all product names, manufactured by Dow Chemical).

[0623] The hydrophobic group of the nonionic surfactant may be any of an alkylphenol group, a linear alkyl group, and a branched alkyl group. For example, the polyoxyethylene alkylphenyl ether-based nonionic compound may be, for example, a compound represented by the following general formula (ii): R 4 -C6H4-OA 2 -H (ii) (In the formula, R 4 is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms, and A 2 is a polyoxyalkylene chain.) Specific examples of the polyoxyethylene alkylphenyl ether-based nonionic compounds include Triton (registered trademark) X-100 (product name, manufactured by Dow Chem...

Claims

1. A tetrafluoroethylene-based polymer composition for producing a composite sheet to be used as a binder for an electrochemical device, the tetrafluoroethylene-based polymer composition having an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less.

2. Contains a tetrafluoroethylene-based polymer, 2. The tetrafluoroethylene-based polymer composition according to claim 1, wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a tetrafluoroethylene homopolymer and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

3. 3. The tetrafluoroethylene polymer composition according to claim 1, in the form of a powder.

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

5. A binder for electrochemical devices for producing a composite sheet, the binder consisting essentially of a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition has an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less.

6. the tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer, 6. The binder for electrochemical devices according to claim 5, wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a homopolymer of tetrafluoroethylene and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

7. 7. The binder for electrochemical devices according to claim 5, wherein the tetrafluoroethylene polymer composition has an apparent density of 0.40 g / ml or less.

8. 7. The binder for electrochemical devices according to claim 5, wherein the tetrafluoroethylene-based polymer composition is non-melt processable.

9. 7. The binder for electrochemical devices according to claim 5, wherein the tetrafluoroethylene polymer composition contains a fluorine-containing compound having a hydrophilic group.

10. 10. The binder for electrochemical devices according to claim 9, wherein the molecular weight of the fluorine-containing compound having a hydrophilic group is 1,000 or less.

11. 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 -OM ａ (In the formula, M ａ is —H, a metal atom, —NR １ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and 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:

12. 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 atoms are substituted with F, and the alkylene group may contain one or more ether bonds, and some of the H atoms may be substituted with Cl. ０ 10. The binder for electrochemical devices according to claim 9, which is a compound represented by the formula:

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 ionic group is —SO ３ M ａ , -SO ２ M ａ , -PO ３ M ａ and -COOM ａ (In the formula, M ａ is —H, a metal atom, —NR １ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R １ The binder for electrochemical devices according to claim 13, wherein the binder is at least one selected from the group consisting of:

15. 14. The binder for electrochemical devices according to claim 13, wherein the content of the ionic group is 0.8 meq / g or more with respect to the polymer compound.

16. 14. The binder for electrochemical devices according to claim 13, wherein the polymer compound has an ion exchange rate of 53 or less.

17. 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 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; 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 optionally 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 are each independently a single bond or a divalent to decavalent group, T Ｘ and T Ｘ (i) each 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) C containing at least one of said anionic groups. １ ~C ２４ (hydro)(fluoro)carbon groups.)

18. 11. The binder for electrochemical devices according to claim 10, wherein the fluorine-containing compound having a hydrophilic group is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a perfluoroethercarboxylic acid (III) represented by the following general formula (III), and a polymer containing a polymerization unit (1A) based on a monomer represented by the following general formula (1A): General formula (1): (H-(CF) ２ ) ｍ－１ -COO) ｐ M １ (wherein m is 4 to 20. M １ represents 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; and 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. Rf １ -O-(CF(CF ３ )CF ２ O) ｎ３ CF(CF ３ )COOM (III) (wherein, Rf １ is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, M is H, a metal atom, or NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group. CH ２ =CF(-CF ２ -O-Rf-A) (1A) (wherein Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond; A is -COOM ａ , -SO ３ M ａ , -OSO ３ M ａ , -SO ２ M ａ , or C(CF ３ ) ２ O.M. ａ (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.

19. 7. The binder for electrochemical devices according to claim 5 or 6, which is in the form of a powder.

20. 7. The binder for electrochemical devices according to claim 5, which is a binder for lithium ion secondary batteries.

21. A tetrafluoroethylene-based polymer composition for producing a composite sheet used as a binder for an electrochemical device, the tetrafluoroethylene-based polymer composition having an average particle size of 1 μm or more and 300 μm or less, and a proportion of particles having an aspect ratio of 3.0 or more of 15% or less.

22. Contains a tetrafluoroethylene-based polymer, The tetrafluoroethylene-based polymer composition according to claim 21, wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a tetrafluoroethylene homopolymer and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

23. The tetrafluoroethylene polymer composition according to claim 21 or 22, in the form of a powder.

24. The tetrafluoroethylene polymer composition according to claim 21 or 22, which is used as a binder for lithium ion secondary batteries and is in the form of a powder.

25. A binder for electrochemical devices for producing a composite sheet, the binder consisting essentially of a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition has an average particle size of 1 μm or more and 300 μm or less, and the proportion of particles having an aspect ratio of 3.0 or more is 15% or less.

26. the tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer, 26. The binder for electrochemical devices according to claim 25, wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a homopolymer of tetrafluoroethylene and a modified polytetrafluoroethylene containing polymerization units based on tetrafluoroethylene and polymerization units based on hexafluoropropylene.

27. 27. The binder for electrochemical devices according to claim 25 or 26, which is in the form of a powder.

28. 27. The binder for electrochemical devices according to claim 25 or 26, which is a binder for lithium ion secondary batteries.

29. 27. An electrode mixture comprising the tetrafluoroethylene-based polymer composition according to claim 1, 2, 21, or 22, or the binder for electrochemical devices according to claim 5, 6, 25, or 26, and an electrode active material.

30. 30. The electrode mixture according to claim 29, which is in the form of a sheet.

31. 27. An electrode comprising the tetrafluoroethylene-based polymer composition according to claim 1, 2, 21, or 22, or the binder for electrochemical devices according to claim 5, 6, 25, or 26, an electrode active material, and a current collector.

32. A secondary battery comprising the electrode according to claim 31.

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