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

Abstract

Provided are a tetrafluoroethylene-based polymer composition for an electrode binder for an electrochemical device, which enables an electrode mixture tablet having excellent uniformity, and an electrode binder for an electrochemical device, an electrode mixture, an electrode, and a secondary battery using the same. A tetrafluoroethylene-based polymer composition for an electrode binder for an electrochemical device, wherein the average particle diameter of the tetrafluoroethylene-based polymer composition is 1 µm or more and 300 µm or less, and the average aspect ratio is 2.0 or less.

Description

Technical Field

[0001] This disclosure relates to tetrafluoroethylene-based polymer compositions, binders for electrochemical devices, electrode compounds, electrodes, and secondary batteries. Background Technology

[0002] Lithium-ion batteries and other rechargeable batteries are used in small and portable electrical and electronic devices such as laptops, mobile phones, smartphones, tablets, and ultrabooks due to their high voltage, high energy density, low self-discharge, low memory effect, and ability to achieve ultra-lightweight designs. They are also being practically applied as power sources for automotive applications, such as driving power supplies for vehicles or large stationary power supplies. Further improvements in energy density and battery characteristics are needed for rechargeable batteries.

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

[0004] Patent documents 2-7 describe the use of polytetrafluoroethylene as a binder for batteries.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Publication No. 2017-517862

[0008] Patent Document 2: International Publication No. 2021 / 181887

[0009] Patent Document 3: International Publication No. 2021 / 192541

[0010] Patent Document 4: International Publication No. 2022 / 138942

[0011] Patent Document 5: International Publication No. 2022 / 138939

[0012] Patent Document 6: International Publication No. 2022 / 024520

[0013] Patent Document 7: International Publication No. 2023 / 098300 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] The purpose of this disclosure is to provide a tetrafluoroethylene-based polymer composition for an electrochemical device binder that can produce a binder sheet with excellent uniformity, as well as an electrochemical device binder, electrode binder, electrode and secondary battery using the same.

[0016] Methods for solving problems

[0017] This disclosure (1) is a tetrafluoroethylene-based polymer composition used as an adhesive for electrochemical devices, wherein the average particle size of the tetrafluoroethylene-based polymer composition is more than 1 μm and less than 300 μm, and the average aspect ratio is less than 2.0.

[0018] This disclosure (2) is a tetrafluoroethylene-based polymer composition as described in this disclosure (1), wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymerization units and hexafluoropropylene-based polymerization units.

[0019] This disclosure (3) is a tetrafluoroethylene-based polymer composition as described in disclosure (1) or (2), which is in the form of a powder.

[0020] This disclosure (4) comprises a tetrafluoroethylene polymer composition as described in any one of (1) to (3) of this disclosure, which is used as a binder for lithium-ion secondary batteries and is in the form of a powder.

[0021] This disclosure (5) is an adhesive for electrochemical devices, which is essentially composed only of a tetrafluoroethylene-based polymer composition, wherein the average particle size of the tetrafluoroethylene-based polymer composition is more than 1 μm and less than 300 μm, and the average aspect ratio is less than 2.0.

[0022] This disclosure (6) provides an adhesive for electrochemical devices as described in this disclosure (5), wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymerization units and hexafluoropropylene-based polymerization units.

[0023] This disclosure (7) is an adhesive for electrochemical devices as described in disclosure (5) or (6), wherein the apparent density of the tetrafluoroethylene-based polymer composition is less than 0.40 g / ml.

[0024] This disclosure (8) is an adhesive for electrochemical devices as described in any one of (5) to (7) of this disclosure, wherein the tetrafluoroethylene-based polymer composition is non-melt processable.

[0025] This disclosure (9) is an adhesive for electrochemical devices as described in any one of disclosures (5) to (8), wherein the tetrafluoroethylene polymer composition comprises a fluorinated compound having a hydrophilic group.

[0026] This disclosure (10) is an adhesive for electrochemical devices as described in this disclosure (9), wherein the molecular weight of the fluorinated compound having hydrophilic groups is less than 1000.

[0027] This disclosure (11) is an adhesive for electrochemical devices as described in disclosure (9) or (10), wherein the hydrophilic group is selected from -SO3M a -SO2M a -OSO2M a -PO3M a -COOM a -OCOM a and -OM a (where M is in the formula) a -H, metal atom, -NR 1 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 1 It is at least one of the groups consisting of H or organic groups.

[0028] This disclosure (12) provides an adhesive for electrochemical devices as described in any one of disclosures (9) to (11), wherein the fluorinated compound having a hydrophilic group is of the following general formula (N 0 The compound shown is )

[0029] (where X) n0 It can be H, Cl, or F. Rf n0 It is a chain, branched, or cyclic alkylene group with 3 to 20 carbon atoms, in which some or all of the H atoms are replaced by F. The alkylene group may contain one or more ether bonds, and some of the H atoms may be replaced by Cl. 0 (It is an anionic group).

[0030] This disclosure (13) is an adhesive for electrochemical devices as described in this disclosure (9), wherein the fluorinated compound having hydrophilic groups is a polymer compound having ionic groups.

[0031] This disclosure (14) describes an adhesive for electrochemical devices as described in this disclosure (13), wherein the ionic group is selected from -SO3M a -SO2M a -PO3M a and -COOM a (where M is in the formula) a -H, metal atom, -NR 1 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R1 It is at least one of the groups consisting of H or organic groups.

[0032] This disclosure (15) is an adhesive for electrochemical devices as described in disclosure (13) or (14), wherein the content of the ionic groups is 0.8 meq / g or more relative to the polymer compound.

[0033] This disclosure (16) is an adhesive for electrochemical devices as described in any one of disclosures (13) to (15), wherein the ion exchange rate of the polymer compound is 53 or less.

[0034] This disclosure (17) is an adhesive for electrochemical devices as described in any one of disclosures (13) to (16), wherein the polymeric compound is at least one selected from the group consisting of a polymer (I) comprising a polymeric unit (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II).

[0035] General formula (I):

[0036] (where X) 1 and X 3 Each is independently F, Cl, H or CF3; A 0 It is an anionic group; X 2 It is H, F, alkyl or fluorinated alkyl; R is a linking group; Z 1 and Z 2 Each is independently H, F, alkyl, or fluorinated alkyl; m is an integer greater than or equal to 1.

[0037] General Formula (II):

[0038] (in the formula, R FA1 -Rf 1 p -R F -O q -, R FA2 -Rf 2 p -R FX -O q -, R F It is a divalent fluorinated polyether group. R FX It is a divalent fluorinated polyether group containing anionic groups. Rf 1 and Rf 2Each can be independently represented by a C atom that is substituted with one or more fluorine atoms. 1-6 Alkylene p can be 0 or 1 independently. Each q is independently either 0 or 1. X A Each group is independently a single bond or a 2- to 10-valent group. T X and T X Each can be independently selected from (i) C1 to C2 containing one or more of H, O and Cl, and without the aforementioned anionic group. 24 (ii) Hydrogen (fluorine) hydrocarbon group and (ii) C1-C1 groups containing at least one of the aforementioned anionic groups. 24 (A group composed of (hydrogen)(fluorine) hydrocarbon groups).

[0039] This disclosure (18) is an adhesive for electrochemical devices as described in disclosure (10) or (11), wherein the fluorinated compound having a hydrophilic group is at least one selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), a perfluoroether carboxylic acid (III) represented by general formula (III), and a polymer comprising a polymeric unit (1A) based on a monomer represented by general formula (1A).

[0040]

[0041] (In the formula, m ranges from 4 to 20. M) 1 For H, metal atoms, NR 5 4(R 5 They can be the same or different (either H or an organic group with 1 to 10 carbon atoms), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. p is 1 or 2).

[0042]

[0043] (In the formula, n is 4 to 20. M) 2 For H, metal atoms, NR 5 4(R 5 (Same as above), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. q is 1 or 2).

[0044]

[0045] (where Rf) 1 It is a perfluoroalkyl group with 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is as defined above.

[0046]

[0047] (In the formula, Rf is a fluorinated alkylene group with 1 to 40 carbon atoms, or a fluorinated alkylene group with ether bonds having 2 to 100 carbon atoms. A is -COOM) a -SO3M a -OSO3M a -SO2M a Or C(CF3)2OM a (M a -H, metal atom, -NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 (H or organic group).

[0048] The binder for electrochemical devices as described in any one of (5) to (18) of this disclosure (19) is in the form of a powder.

[0049] This disclosure (20) refers to the binder for electrochemical devices as described in any one of (5) to (19) of this disclosure, which is a binder for lithium-ion secondary batteries.

[0050] This disclosure (21) is a tetrafluoroethylene-based polymer composition used as an adhesive for electrochemical devices, wherein the average particle size of the tetrafluoroethylene-based polymer composition is 1 μm or more and 300 μm or less, and the proportion of particles with an aspect ratio of 3.0 or more is 15% or less.

[0051] This disclosure (22) describes a tetrafluoroethylene-based polymer composition as described in this disclosure (21), wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymerization units and hexafluoropropylene-based polymerization units.

[0052] This disclosure (23) comprises a tetrafluoroethylene-based polymer composition as described in disclosure (21) or (22), which is in the form of a powder.

[0053] This disclosure (24) comprises a tetrafluoroethylene polymer composition as described in any one of disclosures (21) to (23), which is used as a binder for lithium-ion secondary batteries and is in the form of a powder.

[0054] This disclosure (25) is an adhesive for electrochemical devices, which is essentially composed only of a tetrafluoroethylene-based polymer composition, wherein the average particle size of the tetrafluoroethylene-based polymer composition is 1 μm or more and 300 μm or less, and the proportion of particles with an aspect ratio of 3.0 or more is 15% or less.

[0055] This disclosure (26) describes an adhesive for electrochemical devices as described in this disclosure (25), wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymerization units and hexafluoropropylene-based polymerization units.

[0056] The binder for electrochemical devices described in this disclosure (27) as in disclosure (25) or (26) is in the form of a powder.

[0057] This disclosure (28) refers to the binder for electrochemical devices as described in any one of disclosures (25) to (27), which is a binder for lithium-ion secondary batteries.

[0058] This disclosure (29) is an electrode compound comprising a tetrafluoroethylene polymer composition as described in any one of (1) to (4) and (21) to (24) of this disclosure, or an electrochemical device binder and electrode active material as described in any one of (5) to (20) and (25) to (28) of this disclosure.

[0059] The electrode mixture described in this disclosure (30) as described in this disclosure (29) is in the form of a tablet.

[0060] This disclosure (31) is an electrode comprising a tetrafluoroethylene polymer composition as described in any one of (1) to (4), (21) to (24) of this disclosure, or an electrochemical device binder, electrode active material and current collector as described in any one of (5) to (20), (25) to (28) of this disclosure.

[0061] This disclosure (32) is a secondary battery having the electrodes described in this disclosure (31).

[0062] Invention Effects

[0063] According to this disclosure, it is possible to provide a tetrafluoroethylene-based polymer composition for an electrochemical device binder that can produce a binder sheet with excellent uniformity, as well as an electrochemical device binder, electrode binder, electrode and secondary battery using the same. Attached Figure Description

[0064] Figure 1This is a schematic diagram showing an example of a conical stirring blade. (a) is an upward-facing conical stirring blade, (b) is a downward-facing conical stirring blade, (c) is a front-joined conical stirring blade, and (d) is a double-conical stirring blade with a circular saw. Detailed Implementation

[0065] 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.

[0066] As the aforementioned organic group, an alkyl group with or without one or more substituents is preferred.

[0067] The following details this disclosure.

[0068] This disclosure provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (1) of this disclosure), which is a tetrafluoroethylene (TFE)-based polymer composition for use as an adhesive in electrochemical devices, wherein the TFE-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.

[0069] This disclosure also provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (2) of this disclosure) for use as an adhesive for electrochemical devices, wherein the TFE-based polymer composition has an average particle size of 1 μm or more and 300 μm or less, and the proportion of particles with an aspect ratio of 3.0 or more is 15% or less.

[0070] In this specification, unless otherwise stated, the TFE-based polymer compositions (1) and (2) of this disclosure are collectively referred to as "TFE-based polymer compositions of this disclosure".

[0071] The TFE-based polymer composition disclosed herein, by having the above-described structure, can produce compound sheets with excellent uniformity (few in-plane deviations). Furthermore, compound sheets with excellent strength and softness can also be obtained.

[0072] Furthermore, the TFE-based polymer compositions disclosed herein can be used dry, thus eliminating the need for large amounts of dispersion media such as water or organic solvents. This allows for a wide selection of electrode active materials and solid electrolytes, which is advantageous in the production process. Additionally, it reduces the number of steps and costs associated with using dispersion media.

[0073] Furthermore, the TFE-based polymer composition disclosed herein exhibits excellent adhesion to active substances and electrolytes, thus enabling a reduction in the amount required.

[0074] The TFE-based polymer composition disclosed herein has an average particle size of 1 μm or more and 300 μm or less. From the viewpoint of obtaining compound tablets with better uniformity, it is preferably 3 μm or more, more preferably 5 μm or more, more preferably 10 μm or more, even more preferably 20 μm or more, even more preferably 30 μm or more, and 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.

[0075] The average particle size was determined using the following laser diffraction method. A dry method was performed using a HELOS & RODOS system (trade name, manufactured by SYMPATEC). For the powder being tested dispersed by compressed air at a dispersion pressure of 2 bar, the particle size distribution of the powder was calculated by sensing the shadow cast by the laser on the powder using a measuring sensor. The average particle size (50% cumulative particle size) D50 was then determined on a volume basis. D50 is equal to the particle size corresponding to 50% of the cumulative particle size distribution.

[0076] The TFE-based polymer composition (1) disclosed herein has an average aspect ratio of 2.0 or less.

[0077] The average aspect ratio of the TFE-based polymer composition (2) disclosed herein is preferably 2.0 or less.

[0078] From the perspective of obtaining compound tablets with better uniformity, the aforementioned 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. Alternatively, the aforementioned average aspect ratio can be 1.0 or more.

[0079] The average aspect ratio was determined by averaging the ratio of the major to minor diameter of the TFE-based polymer composition observed using a scanning electron microscope (SEM). Images of more than 200 randomly selected particles were processed.

[0080] The proportion of particles with an aspect ratio of 3.0 or more in the TFE-based polymer composition (1) disclosed herein is preferably 15% or less.

[0081] The proportion of particles with an aspect ratio of 3.0 or more in the TFE-based polymer composition (2) disclosed herein is 15% or less.

[0082] From the perspective of obtaining compound tablets with better uniformity, the proportion of particles with 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, particularly preferably less than 5%, and the above proportion can be 1% or more.

[0083] For the above proportions, the TFE-based polymer composition was observed using a scanning electron microscope (SEM). More than 200 randomly selected particles were image-processed, and the aspect ratio of each particle was determined based on the ratio of its major diameter to minor diameter. This aspect ratio was then calculated as a proportion relative to the total number of particles selected.

[0084] From the perspective of obtaining a compound tablet with better uniformity, the apparent density of the TFE-based polymer composition disclosed herein is preferably 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 also preferably 0.05 g / ml or more, and also preferably 0.20 g / ml or more.

[0085] The apparent density was determined according to JIS K 6892.

[0086] The TFE-based polymer compositions disclosed herein are preferably non-melt processable.

[0087] In this specification, non-melt processability refers to a melt flow rate (MFR) of less than 0.25 g / 10 min, preferably less than 0.10 g / 10 min, more preferably less than 0.05 g / 10 min, and even more preferably less than 0.01 g / 10 min.

[0088] The above MFR is the value obtained according to ASTM D1238, using a melt indexer at 372°C and a load of 5 kg, as the mass (g / 10 min) of polymer flowing out of a nozzle with an inner diameter of 2.095 mm and a length of 8 mm per 10 minutes.

[0089] The TFE-based polymer compositions disclosed herein comprise TFE-based polymers. These TFE-based polymers can be homopolymers of TFE or TFE copolymers comprising TFE-based polymeric units (TFE units) and polymeric units based on modified monomers capable of copolymerizing with TFE (modified monomer units).

[0090] The aforementioned TFE-based polymers can be polytetrafluoroethylene (PTFE). The aforementioned PTFE includes homopolymers of TFE and modified PTFE containing more than 99.0% by mass of TFE units and less than 1.0% by mass of modified monomer units.

[0091] From the perspective of obtaining compound tablets with better uniformity, strength and softness, the above-mentioned TFE-based polymer is preferably PTFE, and more preferably modified PTFE.

[0092] It should be noted that, in this disclosure, the homopolymer of TFE refers to a polymer in which the content of the modified monomer unit relative to the total polymeric unit is less than 0.0001% by mass.

[0093] From the perspective of obtaining compound tablets with superior uniformity, strength, and softness, the content of modified monomer units relative to all polymer units is preferably in the range of 0.0001 to 10% by mass. As a lower limit for the content of modified monomer units, it is more preferably 0.001% by mass, further preferably 0.010% by mass, even more preferably 0.015% by mass, and particularly preferably 0.020% by mass. As an upper limit for the content of modified monomer units, it is preferably 5.0% by mass, more preferably 3.0% by mass, further 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.

[0094] In this specification, the modified monomer unit refers to a portion of the molecular structure of the TFE-based polymer that is derived from the modified monomer.

[0095] The content of each of the above-mentioned polymerization units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescence X-ray analysis according to the type of monomer.

[0096] As for the aforementioned modified monomers, there are no particular limitations as long as they can copolymerize with TFE. Examples include perfluoroolefins such as hexafluoropropylene [HFP]; hydrofluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as trifluorochloroethylene [CTFE]; perfluorovinyl ethers; perfluoroallyl ethers; (perfluoroalkyl)ethylene; ethylene; and monomers with polar groups. In addition, one or more modified monomers can be used.

[0097] The perfluorovinyl ethers mentioned above are not particularly limited; for example, perfluorounsaturated compounds represented by the following general formula (A) can be cited.

[0098] (where Rf) 1 (This refers to a perfluorinated organic group). In this specification, "perfluorinated organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The aforementioned perfluorinated organic group may contain ether oxygen.

[0099] Examples of perfluorovinyl ethers include, for instance, Rf in general formula (A). 1 The perfluoroalkyl group is a perfluoro(alkyl vinyl ether) [PAVE] with 1 to 10 carbon atoms. The preferred number of carbon atoms in the perfluoroalkyl group is 1 to 5.

[0100] Examples of perfluoroalkyl groups in the aforementioned PAVE include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl.

[0101] As a further example of the aforementioned perfluorovinyl ether, Rf in the above general formula (A) can be cited. 1 Substances with a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms; Rf 1 Substances with groups represented by the following formula; [Chemistry 1]

[0102] (In the formula, m represents 0 or an integer from 1 to 4); Rf 1 Substances containing groups represented by the following formulas, [Chemistry 2]

[0103] (In the formula, n represents an integer from 1 to 4).

[0104] There is no particular limitation as to (perfluoroalkyl)ethylene [PFAE], for example, (perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene, etc.

[0105] Examples of perfluoroallyl ethers include, for example, fluorinated monomers represented by general formula (B).

[0106] (where Rf) 2 (Indicates a perfluorinated organic group).

[0107] The above Rf 2 Preferred are perfluoroalkyl groups having 1 to 10 carbon atoms or perfluoroalkoxyalkyl groups having 1 to 10 carbon atoms. As the above-mentioned perfluoroallyl ether, it is preferably selected from at least one of 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 from at least one of the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9, and even more preferably from CF2=CF-CF2-O-CF2CF2CF3.

[0108] The modified monomers are preferably compounds represented by the following general formula (i).

[0109] (where X) 1 ~X 3 Each can be H or F independently. X 4 It can be F, Cl, Rf, or O-Rf. Rf is a perfluorinated organic group.

[0110] As Rf in general formula (i), a perfluoroalkyl group having 1 to 10 carbon atoms is preferred, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, and a perfluoroalkyl group having 1 to 4 carbon atoms is even more preferred.

[0111] The monomers with polar groups mentioned above can be either non-fluorinated monomers or fluorinated monomers.

[0112] Examples of non-fluorinated monomers include hydroxyl groups such as hydroxyl ethyl vinyl ether, hydroxyl propyl vinyl ether, hydroxyl butyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; non-fluorinated monomers with carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, succinic acid, fumaric acid, crotonic acid, maleic acid, citraconic acid, undecenoic acid, and ethynyl dicarboxylic acid; and itaconic anhydride (hereinafter also referred to as "IAH"), citraconic anhydride (hereinafter also referred to as "CAH"), and 5-norbornene-2- Non-fluorinated monomers with anhydride residues, such as 3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), succinic anhydride, fumaric anhydride, and maleic anhydride; non-fluorinated monomers with sulfonate groups, such as vinyl sulfonic acid; non-fluorinated monomers with epoxy groups (glycidyl groups), such as glycidyl vinyl ether and glycidyl allyl ether; non-fluorinated monomers with amino groups, such as aminoalkyl vinyl ether and aminoalkyl allyl ether; non-fluorinated monomers with amide groups, such as (meth)acrylamide and hydroxymethylacrylamide; and non-fluorinated monomers with nitrile groups, such as acrylonitrile and methacrylonitrile.

[0113] Among them, non-fluorinated monomers having carboxyl groups and non-fluorinated monomers having anhydride residues are preferred, non-fluorinated monomers having anhydride residues are more preferred, and cyclic non-fluorinated monomers having anhydride residues are even more preferred.

[0114] The aforementioned monomers with polar groups also preferably include modified monomers (hereinafter referred to as "modified monomer (A)") having functional groups and hydrophilic groups capable of undergoing free radical polymerization.

[0115] Examples of hydrophilic groups in the aforementioned modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (where M represents H, a metal atom, or NR). 74. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7 It can be an H or an organic group, which can be the same or different. Any two can bond together to form a ring. As the above-mentioned hydrophilic group, -SO3M or -COOM is preferred. As R 7 H or C are preferred 1-10 Organic groups, more preferably H or C 1-4 The organic groups, preferably H or C, are preferred. 1-4 Alkyl groups.

[0116] Examples of metal atoms that can be classified as monovalent or divalent include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0117] As a "functional group capable of undergoing reaction via free radical polymerization" in the aforementioned modified monomer (A), examples include groups with olefinic unsaturated bonds such as vinyl and allyl.

[0118] Groups containing olefinic unsaturated bonds can be represented by the following formula,

[0119] (where X) e X f and X g Each can be independently F, Cl, H, CF3, CF2H, CFH2, or CH3; R is a linking group. Examples of linking groups for R, as described later, can be found... a Linking groups include, preferably, groups with unsaturated bonds such as -CH=CH2, -CF=CH2, -CH=CF2, -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(CF3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, and -O-CF2-CF=CF2.

[0120] The modified monomer (A) described above possesses functional groups capable of undergoing free radical polymerization. Therefore, it is hypothesized that when used in polymerization, it reacts with the fluorinated monomer in the early stages of the polymerization reaction to form particles with hydrophilic groups derived from the modified monomer (A) and high stability. Thus, it is believed that the particle number increases when polymerization is carried out in the presence of the modified monomer (A).

[0121] The modified monomer (A) mentioned above can be used alone or in combination of two or more.

[0122] As the modified monomer (A) mentioned above, a compound having unsaturated bonds can be used.

[0123] The modified monomer (A) is preferably at least one selected from the group consisting of compounds represented by the following formulas (4a) to (4e).

[0124]

[0125] (In the formula, n1 represents an integer from 1 to 10, Y) 3 Indicates -SO3M 1 or -COOM 1 M 1 (Indicates H, NH4, or alkali metal).

[0126]

[0127] (In the formula, n2 represents an integer from 1 to 5, Y) 3 Same as the definition above).

[0128]

[0129] (where X) 1 Let F or CF3 represent n3, where n3 represents an integer from 1 to 10, and Y represents n3. 3 Same as the definition above).

[0130]

[0131] (In the formula, n4 represents an integer from 1 to 10, Y) 3 and X 1 Same as the definition above).

[0132]

[0133] (In the formula, each X) 2 Same, indicating F or H. n5 represents 0 or an integer from 1 to 10, Y 3 Same as the definition above).

[0134] Examples of alkali metals mentioned above include Na and K.

[0135] In the above formula (4a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. From the perspective of obtaining suitable water solubility and surface activity, the above Y... 3 Preferred -COOM 1 From the perspective of minimizing residue as an impurity and improving the heat resistance of the resulting molded article, the above-mentioned M 1 H or NH4 is preferred.

[0136] Examples of perfluorovinylalkyl compounds represented by formula (4a) above include CF2=CFCF2COOM. 1 (where M is in the formula) 1 Same as the definition above).

[0137] In the above formula (4b), from the perspective of emulsifying ability, n2 is preferably an integer of 3 or less, and from the perspective of obtaining suitable water solubility and surface activity, Y 3 Preferred -COOM 1 From the perspective of minimizing residue as an impurity and improving the heat resistance of the resulting molded article, M 1 H or NH4 is preferred.

[0138] In the above formula (4c), from the perspective of water solubility, n3 is preferably an integer of 5 or less; from the perspective of obtaining suitable water solubility and surface activity, the above Y... 3 Preferred -COOM 1 From the perspective of good dispersion stability, the above-mentioned M 1 H or NH4 is preferred.

[0139] In the above equation (4d), from the perspective of surface activity energy, the above X 1 Preferably -CF3, from the perspective of water solubility, the above-mentioned n4 is preferably an integer of 5 or less, and from the perspective of obtaining moderate water solubility and surface activity, the above-mentioned Y 3 Preferred -COOM 1 The above M 1 H or NH4 is preferred.

[0140] Examples of perfluorovinyl ether compounds represented by the above formula (4d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM. 1 (where M is in the formula) 1 (Indicates H, NH4, or alkali metal).

[0141] In the above formula (4e), from the perspective of emulsifying ability, n5 is preferably an integer from 1 to 5, more preferably 0, 1, or 2, and even more preferably 0 or 1. From the perspective of obtaining suitable water solubility and surface activity, the above Y3 Preferred -COOM 1 From the perspective of minimizing residue as an impurity and improving the heat resistance of the resulting molded article, the above-mentioned M 1 H or NH4 is preferred.

[0142] Examples of perfluorovinylalkyl compounds represented by formula (4e) above include CH2=CFCF2OCF(CF3)COOM. 1 , CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM 1 (where M is in the formula) 1 Same as the definition above).

[0143] As the modified monomer mentioned above, from the perspective of improving tensile strength, adhesion and softness of the compound sheet, it is preferred to be at least one selected from the group consisting of HFP, PAVE, PFAE and monomers having polar groups, more preferably 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 anhydride residues and modified monomer (A), further preferably at least one selected from the group consisting of HFP, PMVE, PPVE, cyclic non-fluorinated monomers having anhydride residues and compounds represented by general formula (4e), even more preferably at least one selected from the group consisting of HFP and PPVE, and even more preferably HFP.

[0144] The aforementioned TFE-based polymers can have a core-shell structure. Examples of TFE-based polymers with a core-shell structure include modified PTFE, which contains a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE in the particles. Examples of such modified PTFE include the PTFE described in Japanese Patent Application Publication No. 2005-527652.

[0145] The aforementioned TFE-based polymers are preferably non-melt processable.

[0146] The content of the TFE-based polymer in the TFE-based polymer composition disclosed herein can be 95.0% by mass or more, preferably 98.0% by mass or more, more preferably 99.0% by mass or more, further preferably 99.5% by mass or more, particularly preferably 99.9% by mass or more, and most preferably 99.95% by mass or more.

[0147] The TFE-based polymer compositions disclosed herein may contain fluorinated compounds having hydrophilic groups.

[0148] Examples of hydrophilic groups selected from -SO3M can be cited as examples.a -SO2M a -OSO2M a -PO3M a -COOM a -OCOM a and -OM a (where M is in the formula) a -H, metal atom, -NR 1 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 1 It is at least one of the groups consisting of H or organic groups.

[0149] The hydrophilic groups mentioned above can be ionic groups, preferably anionic groups.

[0150] Examples of fluorinated compounds with hydrophilic groups include those with a molecular weight of 1000 or less, specifically those with a molecular weight of 1000 g / mol or less. The molecular weight of these fluorinated compounds is preferably 800 or less, and more preferably 500 or less.

[0151] Polymer particles obtained by polymerization in the presence of fluorinated surfactants typically contain fluorinated surfactants in addition to TFE-based polymers. In this specification, fluorinated surfactants are used during polymerization.

[0152] The aforementioned fluorinated compounds with a molecular weight of less than 1000 can be compounds that were not added during polymerization, such as compounds that are byproducts produced during polymerization.

[0153] It should be noted that, when referring to fluorinated compounds with a molecular weight of 1000 or less, including both anionic and cationic portions, this means fluorinated compounds in which the molecular weight of the anionic portion is 1000 or less. These fluorinated compounds with a molecular weight of 1000 or less do not include TFE-based polymers.

[0154] Examples of fluorinated compounds with hydrophilic groups and a molecular weight of 1000 or less include fluorinated surfactants (anionic fluorinated surfactants) with anionic moiety and a molecular weight of 1000 or less. The term "anionic moiety" refers to the portion of the fluorinated surfactant other than the cationic moiety. For example, in F(CF2)... n1 In the case of COOM, it is "F(CF2)". n1 The "COO" part.

[0155] Examples of anionic fluorinated surfactants include those of the general formula (N... 0 The compound shown is )

[0156] (where X) n0 It can be H, Cl, or F. Rf n0 Y is a chain, branched, or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H atoms are substituted with F. This alkylene group may contain more than one ether bond, and some of the H atoms may be substituted with Cl. 0 (It is an anionic group).

[0157] Y 0 The anionic group can be -COOM, -SO2M, or -SO3M. M can be H, a metal atom, or NR. 7 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7 It can be H or an organic group. Examples of metal atoms mentioned above include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li. As R... 7 It can be H or C 1-10 The organic group can be H or C. 1-4 The organic group can be H or C. 1-4 Alkyl group. M can be H, a metal atom, or NR. 7 4 can be H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR. 7 4 can be H, Na, K, Li, or NH4. The above Rf n0 In this process, more than 50% of H can be replaced by fluorine.

[0158] As a general formula (N) 0 The compounds shown in the figure can be exemplified by the following compounds: general formula (N 1 The compound shown is )

[0159] (where X) n0 H, Cl, and F are given, m1 is an integer from 3 to 15, and Y is given. 0 As defined above); General formula (N) 2 The compound shown is )

[0160] (where Rf) n1 It is a perfluoroalkyl group with 1 to 5 carbon atoms, m2 is an integer from 0 to 3, and X n1 For F or CF3, Y 0 As defined above); General formula (N) 3 The compound shown is )

[0161] (where Rf) n2 It is an alkyl group with 1 to 13 carbon atoms, which may contain ether bonds or be partially or fully fluorinated, m3 is an integer from 1 to 3, and Rf n3 It is a straight-chain or branched perfluoroalkylene group with 1 to 3 carbon atoms, where q is 0 or 1, and Y is... 0 As defined above); General formula (N) 4 The compound shown is )

[0162] (where Rf) n4 Y is a straight-chain or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and may contain ether bonds and / or chlorine atoms. n1 and Y n2 Same or different, H or F, p is 0 or 1, Y 0 As defined above); General formula (N) 5 The compound shown is ) [Chemistry 3]

[0163] (where X) n2 X n3 and X n4 They can be the same or different, and can be H, F, or a straight-chain or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and containing ether bonds. Rf n5 It is a linear or branched partially or fully fluorinated alkylene group with 1 to 3 carbon atoms, which may contain ether bonds; L is a linking group; Y is a linking group. 0 As defined above. Where, X n2 X n3 X n4 and Rf n5 (The total number of carbon atoms is less than 18); etc.

[0164] As a general formula (N) 0More specifically, examples of compounds represented by formula (I) include perfluorocarboxylic acids (I), ω-H perfluorocarboxylic acids (II), perfluoroether carboxylic acids (III), perfluoroalkylalkylene carboxylic acids (IV), perfluoroalkoxyfluorocarboxylic acids (V), perfluoroalkylsulfonic acids (VI), ω-H perfluorosulfonic acids (VII), perfluoroalkylalkylene sulfonic acids (VIII), alkylalkylene carboxylic acids (IX), fluorocarboxylic acids (X), alkoxyfluorosulfonic acids (XI), compounds represented by formula (XII), and compounds represented by formula (XIII) below.

[0165] The perfluorocarboxylic acid (I) mentioned above is a substance represented by general formula (I).

[0166] (In the formula, n1 is an integer from 3 to 14, M is H, metal atom, NR) 7 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7 (H or organic groups).

[0167] The above-mentioned ω-H perfluorocarboxylic acid (II) is a substance represented by general formula (II).

[0168] (In the formula, n2 is an integer from 4 to 15, and M is as defined above).

[0169] The above-mentioned perfluoroether carboxylic acid (III) is a substance represented by general formula (III).

[0170] (where Rf) 1 It is a perfluoroalkyl group with 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is as defined above.

[0171] The above-mentioned perfluoroalkylalkylene carboxylic acids (IV) are substances represented by general formula (IV).

[0172] (where Rf) 2 It is a perfluoroalkyl group with 1 to 5 carbon atoms, Rf 3 It is a straight-chain or branched perfluoroalkylene group with 1 to 3 carbon atoms, where n4 is an integer from 1 to 3, and M is as defined above.

[0173] The above-mentioned alkoxyfluorocarboxylic acid (V) is a substance represented by the general formula (V).

[0174] (where Rf) 4 Y is a straight-chain or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and may contain ether bonds and / or chlorine atoms. 1 and Y 2 Same or different, H or F, M as defined above).

[0175] The perfluoroalkyl sulfonic acid (VI) mentioned above is a substance represented by general formula (VI).

[0176] (In the formula, n5 is an integer from 3 to 14, and M is as defined above).

[0177] The above-mentioned ω-H perfluorosulfonic acid (VII) is a substance represented by general formula (VII).

[0178] (In the formula, n6 is an integer from 4 to 14, and M is as defined above).

[0179] The above-mentioned perfluoroalkylalkylene sulfonic acid (VIII) is a substance represented by the general formula (VIII).

[0180] (where Rf) 5 It is a perfluoroalkyl group with 1 to 13 carbon atoms, n7 is an integer from 1 to 3, and M is as defined above.

[0181] The above-mentioned alkylalkylene carboxylic acids (IX) are substances represented by the general formula (IX).

[0182] (where Rf) 6 It is a straight-chain or branched partially or fully fluorinated alkyl group with 1 to 13 carbon atoms, which may contain ether bonds, n8 is an integer from 1 to 3, and M is as defined above).

[0183] The aforementioned fluorocarboxylic acid (X) is a substance represented by the general formula (X).

[0184] (where Rf) 7 Rf is a straight-chain or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and may contain ether bonds and / or chlorine atoms. 8 M is a straight-chain or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms (as defined above).

[0185] The above-mentioned alkoxyfluorosulfonic acid (XI) is a substance represented by the general formula (XI).

[0186] (where Rf) 9 Y is a linear or branched alkyl group with 1 to 12 carbon atoms, which may contain ether bonds and may be partially or fully fluorinated with chlorine. 1 and Y 2 Same or different, H or F, M as defined above).

[0187] The above-mentioned compound (XII) is a substance represented by the general formula (XII). [Chemistry 4]

[0188] (where X) 1 X 2 and X 3 They can be the same or different, and are H, F, and linear or branched partially or fully fluorinated alkyl groups containing ether bonds, with 1 to 6 carbon atoms; Rf 10 It is a perfluoroalkylene group with 1 to 3 carbon atoms, where L is a linking group and Y is a carbon atom group. 0 (It is an anionic group). Y 0 It can be -COOM, -SO2M, or -SO3M, or -SO3M or COOM (where M is as defined above). As L, examples include single bonds, partially or fully fluorinated alkylene groups containing ether bonds with 1 to 10 carbon atoms.

[0189] The above-mentioned compound (XIII) is a substance represented by the following general formula (XIII).

[0190] (where Rf) 11 It is a fluoroalkyl group containing chlorine with 1 to 5 carbon atoms, where n9 is an integer from 0 to 3, n10 is an integer from 0 to 3, and M is as defined above. Examples of compounds (XIII) include CF2ClO (CF2CF(CF3)O). n9 (CF2O) n10 CF2COONH4 (a mixture of average molecular weight 750, where n9 and n10 are as defined above).

[0191] Thus, examples of anionic fluorinated surfactants include carboxylic acid surfactants and sulfonic acid surfactants.

[0192] Fluorinated surfactants can be a single fluorinated surfactant or a mixture containing two or more fluorinated surfactants.

[0193] Examples of fluorinated surfactants include compounds represented by the following formulas. Fluorinated surfactants can be mixtures of these compounds.

[0194] 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 [Chemistry 5]

[0195] (In each formula, M represents H, a metal atom, and NR) 7 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphatonium with or without substituents. R 7 (H or organic groups).

[0196] In the above formulas, M can be H, a metal atom, or NR. 7 4 can be H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR. 7 4 can be H, Na, K, Li or NH4.

[0197] R 7 It can be H or C 1-10 The organic group can be H or C. 1-4 The organic group can be H or C. 1-4 Alkyl groups.

[0198] The content of the aforementioned anionic fluorinated surfactant relative to the aforementioned TFE-based polymer composition is preferably 25 ppb or less by mass, more preferably 20 ppb or less by mass, even more preferably 15 ppb or less by mass, even more preferably 10 ppb or less by mass, even more preferably less than 10 ppb by mass, even more preferably less than 1 ppb by mass, 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 can be an amount less than the lower limit of quantitation.

[0199] The amount of the above-mentioned anionic fluorinated surfactant was determined by the following method.

[0200] Weigh 1 g of the sample, add 10 g (12.6 ml) of methanol, and sonicate for 60 minutes to obtain an extract. Concentrate the extract by purging with nitrogen. Analyze the fluorine-containing compounds in the concentrated extract using LC / MS / MS. Select the molecular weight information from the obtained LC / MS spectrum to confirm its consistency with the structural formula of the candidate fluorine-containing compounds. Prepare aqueous solutions of the standard substance at five or more levels of concentration, and perform LC / MS analysis on each concentration. Plot the relationship between the concentration and the area of ​​the region relative to that concentration to create a calibration curve. Using the calibration curve, convert the area of ​​the LC / MS chromatogram of the fluorine-containing compounds in the extract into the concentration of the fluorine-containing compounds.

[0201] It should be noted that the limit of quantitation in this assay method is 10 ppb by mass.

[0202] TFE-based polymer compositions containing anionic fluorinated surfactants are obtained, for example, by polymerization of anionic fluorinated surfactants.

[0203] As a fluorinated compound with a molecular weight of less than 1000 and containing a hydrophilic group, the following compound (hereinafter also referred to as compound (1)) can also be cited.

[0204]

[0205] (In the formula, m ranges from 4 to 20. M) 1 For H, metal atoms, NR 5 4(R 5 They can be the same or different (either H or an organic group with 1 to 10 carbon atoms), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. p is 1 or 2).

[0206] As M 1 H is preferred.

[0207] As M 1Metal atoms can be categorized into monovalent and divalent metal atoms, and can include alkali metals (Group 1) or alkaline earth metals (Group 2). Specifically, examples include Na, K, and Li.

[0208] 4 Rs 5 They can be the same or different. As R... 5 Preferably, it contains H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0209] 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 preferably 18 or less, even more preferably 16 or less.

[0210] The TFE-based polymer composition disclosed herein may contain one or more compounds (1), or two or more compounds, or three or more compounds.

[0211] The content of compound (1) (in the case of two or more compounds, the content of each component) relative to the above-mentioned TFE polymer can be less than 10 ppm by mass, preferably less than 5000 ppb by mass, more preferably less than 1000 ppb by mass, even more preferably less than 500 ppb by mass, even more preferably less than 100 ppb by mass, even more preferably less than 50 ppb by mass, even more preferably less than 25 ppb by mass, and particularly preferably less than 10 ppb by mass.

[0212] The lower limit is not specifically limited and can be either 0.1 ppb or 1 ppb.

[0213] As fluorinated compounds with hydrophilic groups and a molecular weight of less than 1000, the following general formula (2) can also be cited as examples (hereinafter also referred to as compound (2)).

[0214]

[0215] (In the formula, n is 4 to 20. M) 2 For H, metal atoms, NR 5 4(R 5 (Same as above), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. q is 1 or 2).

[0216] As M 2 H is preferred.

[0217] As M 2Metal atoms can be categorized into monovalent and divalent metal atoms, and can include alkali metals (Group 1) or alkaline earth metals (Group 2). Specifically, examples include Na, K, and Li.

[0218] 4 Rs 5 They can be the same or different. As R... 5 Preferably, it contains H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0219] In general formula (2), n is preferably 6 or more, more preferably 8 or more, further preferably 11 or more, even more preferably 13 or more, particularly preferably 15 or more, and preferably 18 or less, more preferably 16 or less.

[0220] The TFE-based polymer composition disclosed herein may contain one or more compounds (2), or two or more compounds, or three or more compounds.

[0221] The content of compound (2) (in the case of two or more compounds, the content of each component) relative to the above-mentioned TFE-based polymer can be less than 10 ppm by mass, preferably less than 5000 ppb by mass, more preferably less than 1000 ppb by mass, even more preferably less than 500 ppb by mass, even more preferably less than 100 ppb by mass, even more preferably less than 50 ppb by mass, even more preferably less than 25 ppb by mass, even more preferably less than 10 ppb by mass, 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 can be an amount less than the lower limit of quantitation.

[0222] The TFE-based polymer composition comprising compounds (1) and / or (2) is obtained by using a hydrocarbon surfactant. The TFE-based polymer composition disclosed herein may comprise a TFE-based polymer, compounds (1) and / or (2), and a hydrocarbon surfactant. The content of the hydrocarbon surfactant in the above-described TFE-based polymer composition is not particularly limited, but is typically 100 ppm to 10% by mass.

[0223] In the above-mentioned hydrocarbon surfactants, the proportion of hydrogen atoms bonded to carbon atoms that are replaced by fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0224] The TFE-based polymer compositions disclosed herein preferably do not substantially contain the compounds represented by the following general formula (3) (hereinafter also referred to as compound (3)).

[0225]

[0226] (where M is in the formula) 2 For H, metal atoms, NR 5 4(R 5 The groups can be the same or different, and can be H or an organic group with 1 to 10 carbon atoms (preferably a fluorine-free organic group), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. q is 1 or 2).

[0227] "Substantially not containing compound (3)" means that the content of compound (3) is 25 ppb or less by mass relative to the above-mentioned TFE-based polymer. The content of compound (3) is preferably 20 ppb or less by mass relative to the above-mentioned TFE-based polymer, more preferably 15 ppb or less by mass, and even more preferably 10 ppb or less by mass. The lower limit is not particularly limited and can be 0 ppb by mass, 0.1 ppb by mass, or 1 ppb by mass.

[0228] The contents of compounds (1), (2) and (3) were determined using liquid chromatography-mass spectrometry, as described in the examples described later.

[0229] Examples of fluorinated compounds with hydrophilic groups include fluorinated compounds with a molecular weight exceeding 1000, i.e., fluorinated compounds with a molecular weight exceeding 1000 g / mol.

[0230] Examples of fluorinated compounds with hydrophilic groups and molecular weights exceeding 1000 include polymers with ionic groups.

[0231] It should be noted that the TFE-based polymers mentioned above are not included in the aforementioned polymer compounds.

[0232] As for the aforementioned ionic groups, anionic groups are preferred, such as sulfate groups and -COOM groups. 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. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 (e.g., H or organic groups).

[0233] Among them, the preferred option is to select SO3M. a -SO2Ma -PO3M a and -COOM a At least one of the constituent groups, more preferably -COOM a .

[0234] The content of the aforementioned ionic groups relative to the aforementioned 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. Alternatively, the aforementioned content may be 10.0 meq / g or less, 8.00 meq / g or less, or 5.00 meq / g or less.

[0235] The content of the aforementioned ionic groups can be calculated from the composition of the aforementioned polymer compounds.

[0236] The aforementioned polymer preferably contains fluorine atoms, and the proportion in which hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms is preferably 50% or more. The "proportion in which hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms" is determined by the ratio of the number of fluorine atoms to the total number of hydrogen atoms bonded to carbon atoms and the total number of halogen atoms (including fluorine atoms) bonded to carbon atoms. The proportion in which hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms in the aforementioned polymer is not particularly limited, but is more preferably 70% or more, further preferably 80% or more, even more preferably 90% or more, particularly preferably 95% or more, and most preferably 100%.

[0237] The aforementioned polymeric compounds preferably have an ion exchange ratio (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the main chain of the polymeric compound relative to the ionic group. For the purpose of determining the IXR, precursor groups that become ionic through hydrolysis (e.g., -SO2F) are not considered ionic groups.

[0238] The aforementioned IXR is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, even more preferably 4 or more, and particularly more preferably 5 or more. Furthermore, the IXR is preferably 43 or less, more preferably 33 or less, and even more preferably 23 or less.

[0239] In the aforementioned polymeric compounds, ionic groups are typically distributed along the polymer backbone. These polymeric compounds also contain repeating side chains bonded to the polymer backbone, which preferably have ionic groups.

[0240] The aforementioned polymeric compounds are preferably water-soluble polymeric compounds. "Water-soluble" refers to the property of easily dissolving or dispersing in an aqueous medium. Water-soluble polymeric compounds cannot be determined by, for example, dynamic light scattering (DLS) methods, or exhibit particle sizes smaller than 5 nm. On the other hand, water-insoluble polymeric compounds can be determined by, for example, dynamic light scattering (DLS) methods, to have particle sizes larger than 5 nm.

[0241] The number-average molecular weight of the aforementioned polymers is preferably greater than 0.1 × 10⁻⁶. 4 More preferably, it is 0.15×10 4 The above is further preferred to be 0.2×10 4 The above is further preferred to be 0.3×10 4 The above is further preferred to be 0.5×10 4 The above, and especially preferred, is 1.0 × 10 4 The above is particularly preferred, with 2.0×10⁻⁶ being the optimal value. 4 The optimal value is 3.0 × 10⁻⁶. 4 That's all. Additionally, 75.0 × 10 is preferred. 4 The following is more preferably 50.0 × 10 4 The following is a further preferred value: 40.0 × 10 4 Hereinafter, 30.0 × 10 is particularly preferred. 4 The following is particularly preferred: 20.0 × 10 4 the following.

[0242] The weight-average molecular weight of the aforementioned polymers is preferably greater than 0.1 × 10⁻⁶. 4 More preferably, it is 0.2 × 10⁻⁶. 4 The above is further optimized to be 0.4 × 10⁻⁶. 4 The above is further preferred to be 0.6×10 4 The above is further preferred to be 1.0 × 10 4 The above is particularly preferred, with 2.0×10⁻⁶ being the optimal value. 4 The optimal value is 5.0 × 10⁻⁶. 4 That's all. Additionally, 150.0 × 10 is preferred. 4 Hereinafter, 100.0 × 10 is more preferred. 4 The following is a further preferred value: 80.0 × 10 4 Hereinafter, 60.0 × 10 is particularly preferred. 4 The following is particularly preferred: 40.0 × 10 4 the following.

[0243] The number-average molecular weight and weight-average molecular weight mentioned above were calculated using gel permeation chromatography (GPC) with monodisperse polystyrene or monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) as standards. Alternatively, if GPC is not feasible, the number-average molecular weight of the aforementioned polymers can be determined by the correlation between the number-average molecular weight calculated from the number of terminal groups obtained from NMR, FT-IR, etc., and the melt flow rate. The melt flow rate can be measured according to JIS K7210.

[0244] The aforementioned polymeric compound preferably does not substantially contain fractions with a molecular weight of less than 1,000, more preferably does not substantially contain fractions with a molecular weight of less than 1,500, even more preferably does not substantially contain fractions with a molecular weight of less than 2,000, and particularly preferably does not substantially contain fractions with a molecular weight of less than 3,000.

[0245] The absence of the aforementioned fractions means that the content of the aforementioned fractions relative to the aforementioned polymeric compound is 3.0% by mass or less. The content of the aforementioned fractions relative to the aforementioned polymeric compound is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0246] The content of the above fractions can be determined by gel permeation chromatography (GPC) or liquid chromatography-mass spectrometry (LC-MS).

[0247] The aforementioned polymeric compound preferably does not substantially contain fluorinated compounds with a molecular weight of 1000 or less. "Substantially does not contain the aforementioned fluorinated compounds" means that the amount of the aforementioned fluorinated compounds is 25 ppb or less by mass relative to the aforementioned polymeric compound.

[0248] The amount of the aforementioned fluorinated compound is more preferably less than 25 ppb by mass, further preferably less than 10 ppb by mass, even more preferably less than 10 ppb by mass, even more preferably less than 5 ppb by mass, even more preferably less than 3 ppb by mass, even more preferably less than 1 ppb by mass, and particularly preferably less than 1 ppb by mass. The lower limit is not particularly limited and can be an amount less than the detection limit.

[0249] The fluorinated compounds with a molecular weight of less than 1000 and their quantitative methods are described later.

[0250] The aforementioned polymeric compound is preferably selected from at least one of a polymer (I) comprising 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).

[0251] General formula (I):

[0252] (where X)1 and X 3 Each is independently F, Cl, H or CF3; A 0 It is an anionic group; X 2 It is H, F, alkyl or fluorinated alkyl; R is a linking group; Z 1 and Z 2 Each is independently H, F, alkyl, or fluorinated alkyl; m is an integer greater than or equal to 1.

[0253] General Formula (II):

[0254] (in the formula, R FA1 -Rf 1 p -R F -O q -, R FA2 -Rf 2 p -R FX -O q -, R F It is a divalent fluorinated polyether group. R FX It is a divalent fluorinated polyether group containing anionic groups. Rf 1 and Rf 2 Each can be independently represented by a C atom that is substituted with one or more fluorine atoms. 1-6 Alkylene p can be 0 or 1 independently. Each q is independently either 0 or 1. X A Each group is independently a single bond or a 2- to 10-valent group. T X and T X Each can be independently selected from (i) C1 to C2 groups containing one or more of H, O, and Cl, and without the aforementioned anionic groups. 24 (i) Hydrogen (fluorine) hydrocarbon group and (ii) C1-C1 groups containing at least one of the above-mentioned anionic groups. 24 (A group composed of (hydrogen)(fluorine) hydrocarbon groups).

[0255] Polymer (I) is a polymer comprising polymeric units (I) based on monomer (I). Monomer (I) is represented by the following general formula (I).

[0256]

[0257] (where X) 1and X 3 Each is independently F, Cl, H or CF3; X 2 It is H, F, alkyl, or fluorinated alkyl; A 0 R is an anionic group; R is a linking group; Z is an anionic group. 1 and Z 2 Each is independently H, F, alkyl, or fluorinated alkyl; m is an integer greater than or equal to 1.

[0258] As X 2 F, Cl, H, or CF3 are preferred. Additionally, as Z... 1 and Z 2 F or CF3 is preferred.

[0259] In this disclosure, the anionic group includes not only anionic groups such as sulfate groups and carboxyl groups, but also functional groups that provide anionicity, such as acid groups like -COOH and acid salt groups like -COONH4. Preferably, the anionic group is a sulfate group, carboxyl group, phosphate group, phosphonate group, sulfonate group, sulfinate group, or -C(CF3)2OM. a (where M is in the formula) a -H, metal atom, -NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 (H or organic groups).

[0260] In this disclosure, one or more monomers may be used as monomer (I) represented by general formula (I).

[0261] R stands for linking group. In this disclosure, "linking group" refers to a (m+1) valent linking group, where m is 1, indicating a divalent linking group. The linking group can be a single bond, preferably containing at least one carbon atom. The number of carbon atoms can be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. There is no upper limit; for example, it can be less than 100 or less than 50.

[0262] The linking group can be chain-like or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and may contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may contain one or more functional groups selected from the group consisting of esters, amides, sulfonamides, carbonyl groups, carbonates, urethanes, ureas, and carbamates, as desired. The linking group may not contain a carbon atom but may be a spurious heteroatom such as oxygen, sulfur, or nitrogen.

[0263] m is an integer greater than or equal to 1, preferably 1 or 2, more preferably 1. When m is an integer greater than or equal to 2, Z 1 Z 2 and A 0 They can be the same or different.

[0264] Next, the preferred configuration when m is 1 in general formula (I) will be explained.

[0265] R is preferably a suspended heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0266] Polymer (I) is also preferably highly fluorinated. For example, it is preferred that, in addition to the phosphate group moiety (e.g., CH2OP(O)(OM), it is also preferred that...) a )2) and sulfate group (e.g., CH2OS(O)2OM) a Such anionic groups (A) 0 In addition to ), more than 80%, more than 90%, more than 95%, or 100% of the CH bonds in polymer (I) are replaced by CF bonds.

[0267] The monomer (I) and polymer (I) are also preferably free of anionic groups (A). 0 In addition to ), it also has CF bonds but no CH bonds. That is, in the preferred general formula (I), X 1 X 2 and X 3 All of the components are F, and R is a perfluoroalkyl group having 1 or more carbon atoms. The perfluoroalkyl group can be either chain-like or branched, cyclic or acyclic, and may contain at least one spurious heteroatom. The number of carbon atoms in the perfluoroalkyl group can be 2 to 20, or 4 to 18.

[0268] The monomer (I) and polymer (I) can be partially fluorinated. That is, the monomer (I) and polymer (I) are also preferably free of anionic groups (A). 0 In addition to having at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom, it also has at least one hydrogen atom bonded to a carbon atom.

[0269] Anionic group (A) 0 ) can be -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 is preferred. a -OSO3M a -COOM a -P(O)(OM) a )2 or C(CF3)2OM a , more preferably -COOM a -SO3M a -OSO3M a Or C(CF3)2OM a Further optimization of -SO3M a -COOM a or P(O)(OM) a )2, Specially Preferred - SO3M a or COOM a Optimal Selection - COOM a .

[0270] M a For H, metal atoms, NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 It is an H or an organic group.

[0271] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0272] As M a Preferred -H, metal atoms or NR 2 4, more preferably -H, alkali metals (Group 1), alkaline earth metals (Group 2) or NR 2 4. Further preferred are -H, -Na, -K, -Li or NH4, even more preferred are -H, -Na, -K or NH4, particularly preferred are -H, -Na or NH4, and most preferred are -H or NH4.

[0273] In polymer (I), each polymer unit (I) may have different anionic groups or the same anionic groups.

[0274] The monomer (I) is also preferably the monomer shown in general formula (Ia).

[0275] Polymer (I) is also preferably a polymer comprising a polymeric unit (Ia) based on a monomer represented by the general formula (Ia).

[0276]

[0277] (where A is in the formula) 0 It is an anionic group, Rf 0 Perfluorinated, can be chain-like or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and can be arbitrarily supplemented with a perfluorinated divalent linker containing one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen.

[0278] The monomer (I) is also preferably the monomer shown in general formula (Ib).

[0279] Polymer (I) is also preferably a polymer comprising a polymeric unit (Ib) based on a monomer represented by the general formula (Ib).

[0280]

[0281] (where A is in the formula) 0 It is an anionic group, Rf 0 (The perfluorinated divalent linker as defined in formula Ia).

[0282] In general formula (I), A 0 Using sulfate groups is one of the preferred methods. A 0 For example, -CH2OSO3M a -CH2CH2OSO3M a or -SO2NR'CH2CH2OSO3M a In the formula, R' is H or an alkyl group having 1 to 4 carbon atoms, and M... a Same as above.

[0283] A 0 In the case of a sulfate group, as a monomer represented by the general formula (I), examples 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 ) etc. In the above formula, M a Same as above.

[0284] In general formula (I), A 0 Using a sulfonate group is also a preferred method. As A 0 For example, -SO3M a In the formula, M a Same as above.

[0285] A 0 In the case of a sulfonate group, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2SO3M). a ), CF2=CF(O(CF2)3SO3M a ), CF2=CF(O(CF2)4SO3M a ), CF2=CF(OCF2CF(CF3)SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M a CH2=CH(OCF2CF2SO3M) a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M a CH2=CH(O(CF2)4SO3M) a CH2=CH(O(CF2)3SO3M) a ) etc. In the above formula, M a Same as above.

[0286] In general formula (I), A 0 Using a sulfite group is also a preferred method. As A 0 For example, -SO2M a In the formula, M a Same as above.

[0287] A0 In the case of a sulfinate group, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2SO2M). a ), CF2=CF(O(CF2)3SO2M a ), CF2=CF(O(CF2)4SO2M a ), CF2=CF(OCF2CF(CF3)SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO2M a CH2=CH(OCF2CF2SO2M) a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2M a CH2=CH(O(CF2)4SO2M) a CH2=CH(O(CF2)3SO2M) a ) etc. In the above formula, M a Same as above.

[0288] In general formula (I), A 0 Using a carboxylate group is also a preferred method. As A 0 For example, COOM a or SO2NR'CH2COOM a In the formula, R' is H or an alkyl group having 1 to 4 carbon atoms, and M... a Same as above. A 0 In the case of a carboxyl group, as a monomer represented by the general formula (I), CF2=CF(OCF2CF2COOM) can be cited as an example. 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>1), CH2=CH(OCF2CF2COOM) a CH2=CH(O(CF2)4COOM) a CH2=CH(O(CF2)3COOM) a ), CF2=CF(OCF2CF2SO2NR'CH2COOM a ), CF2=CF(O(CF2)4SO2NR'CH2COOMa ), CF2=CF(OCF2CF(CF3)SO2NR'CH2COOM a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR'CH2COOM a ), CH2=CH(OCF2CF2SO2NR'CH2COOM a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR'CH2COOM a ), CH2=CH(O(CF2)4SO2NR'CH2COOM a ), CH2=CH(O(CF2)3SO2NR'CH2COOM a ) etc. In the above formula, R' is H or an alkyl group having 1 to 4 carbon atoms, M a Same as above.

[0289] In general formula (I), A 0 Using phosphate groups is also a preferred method. As A 0 For example, -CH2OP(O)(OM a )2、[-CH2O]2P(O)(OM a -CH2CH2OP(O)(OM) a )2、[-CH2CH2O]2P(O)(OM a ), [-SO2NR'CH2CH2O]2P(O)(OM a ) or SO2NR'CH2CH2OP(O)(OM a )2, where R' is an alkyl group with 1 to 4 carbon atoms, M a Same as above.

[0290] A 0 In the case of a phosphate ester, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2CH2OP(O)(OM). a )2), CF2=CF(O(CF2)4CH2OP(O)(OM a )2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OMa )2), CH2=CH(OCF2CF2CH2OP(O)(OM a )2), CH2=CH(O(CF2)4CH2OP(O)(OM a )2), CH2=CH(O(CF2)3CH2OP(O)(OM a )2) etc. In the above formula, M a Same as above.

[0291] In general formula (I), A 0 Phosphonate groups are also a preferred option. A 0 In the case of a phosphonate group, examples of monomers represented by the general formula (I) include 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), where M a Same as above.

[0292] The monomer (I) is preferably the monomer (1) shown in general formula (1).

[0293] The polymer (I) is preferably a polymer (1) comprising a polymer unit (1) based on a monomer represented by the general formula (1).

[0294]

[0295] (In the formula, X may be the same or different and is -H or F; Y may be -H, -F, alkyl, or fluoroalkyl; Z may be the same or different and is -H, -F, alkyl, or fluoroalkyl. Rf is a fluoroalkylene group with 1 to 40 carbon atoms, or a fluoroalkylene group with ether bonds having 2 to 100 carbon atoms. A is -COOM) a -SO3M a -OSO3M a -SO2M a Or C(CF3)2OM a (M a -H, metal atom, -NR 24. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 (H or an organic group). Among them, at least one of X, Y and Z contains a fluorine atom.

[0296] In the manufacturing method disclosed herein, the monomer (1) shown in general formula (1) can be copolymerized with other monomers.

[0297] The polymer (1) can be a homopolymer of the monomer (1) shown in general formula (1), or a copolymer of other monomers.

[0298] The aforementioned fluorinated alkylene groups with 2 to 100 carbon atoms and ether bonds are alkylene groups that do not have oxygen atoms at the end but contain ether bonds between carbon atoms.

[0299] In general formula (1), X is -H or F. X can be both -F or at least one -H. For example, one can be -F and the other -H, or both can be -H.

[0300] In general formula (1), Y is -H, -F, alkyl, or fluorinated alkyl. The alkyl group is an alkyl group without fluorine atoms, and has 1 or more carbon atoms. The alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. The fluorinated alkyl group is an alkyl group containing at least one fluorine atom, and has 1 or more carbon atoms. The fluorinated alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. Y is preferably -H, -F, or CF3, more preferably -F.

[0301] In general formula (1), Z can be the same or different, and can be -H, -F, alkyl, or fluoroalkyl. The alkyl group is an alkyl group without fluorine atoms, and has 1 or more carbon atoms. The alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. The fluoroalkyl group is an alkyl group containing at least one fluorine atom, and has 1 or more carbon atoms. The fluoroalkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. Z is preferably -H, -F, or CF3, more preferably -F.

[0302] In general formula (1), at least one of X, Y and Z contains a fluorine atom. For example, X could be -H and Y and Z could be -F.

[0303] In general formula (1), Rf is a fluorinated alkylene group with 1 to 40 carbon atoms, or a fluorinated alkylene group with ether bonds with 2 to 100 carbon atoms.

[0304] The number of carbon atoms in the aforementioned fluorinated alkylene group is preferably 2 or more. Furthermore, the number of carbon atoms in the aforementioned fluorinated alkylene group is preferably 30 or less, more preferably 20 or less, further preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. Examples of the aforementioned fluorinated alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CF2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The aforementioned fluorinated alkylene group is preferably a perfluoroalkylene group.

[0305] The fluorinated alkylene group having an ether bond preferably has 3 or more carbon atoms. Furthermore, the fluorinated alkylene group having an ether bond preferably has 60 or fewer carbon atoms, more preferably 30 or fewer, further preferably 12 or fewer, particularly preferably 9 or fewer, and most preferably 6 or fewer. The fluorinated alkylene group having an ether bond is also preferably, for example, a divalent group represented by the following general formula. [Chemistry 6]

[0306] (where Z) 1 For F or CF3; Z 2 and Z 3 H or F respectively; Z 4 (where H, F, or CF3 are integers; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0307] Specifically, examples of fluorinated alkylene groups with ether bonds include -CF2CF(CF3)OCF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, and -(CF(CF3)CF2-O). n -CF(CF3)- (where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n -CF(CF3)CH2- (where n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorinated alkylene groups with ether bonds mentioned above are preferably perfluoroalkylene groups.

[0308] In general formula (1), A is -COOM a -SO3M a -OSO3Ma -SO2M a Or C(CF3)2OM a (M a For H, metal atoms, NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 (H or organic groups).

[0309] As R 2 H or C are preferred 1-10 Organic groups, more preferably H or C 1-4 The organic groups, preferably H or C, are preferred. 1-4 Alkyl groups.

[0310] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0311] As M a H, metal atoms or NR are preferred. 2 4. More preferably, H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR. 2 4. Further preferred materials are H, Na, K, Li or NH4, even more preferred materials are H, Na, K or NH4, particularly preferred materials are H, Na or NH4, and most preferred materials are H or NH4.

[0312] As A, preferred -COOM a Or SO3M a , more preferably -COOM a .

[0313] As a monomer represented by general formula (1), for example, a monomer represented by general formula (1a) can be exemplified.

[0314] (In the formula, each X is the same, representing F or H. n5 represents 0 or an integer from 1 to 10, and A is the same as defined above).

[0315] In general formula (1a), from the perspective of obtaining particles with small primary particle size, n5 is preferably an integer from 0 or 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1.

[0316] In the manufacturing method disclosed herein, the monomer shown in general formula (1a) can be copolymerized with other monomers.

[0317] The polymer (1) can be a homopolymer of the monomers represented by the general formula (1a) or a copolymer of other monomers.

[0318] The monomer (1) is preferably the monomer shown in general formula (1A).

[0319] The polymerization unit (1) is preferably a polymerization unit (1A) based on the monomer shown in general formula (1A).

[0320]

[0321] (In the formula, Rf and A are the same as above).

[0322] In the manufacturing method disclosed herein, the monomer represented by general formula (1A) can be copolymerized with other monomers.

[0323] The polymer (1) can be a homopolymer of the monomers represented by the general formula (1A) or a copolymer of other monomers.

[0324] As a monomer represented by formula (1A), specifically, monomers represented by the following general formula can be cited as examples. [Chemistry 7]

[0325] (where Z) 1 For F or CF3; Z 2 and Z 3 H or F respectively; Z 4 Let H, F, or CF3 be the integers p1+q1+r1 from 0 to 10; s1 be 0 or 1; t1 be an integer from 0 to 5, where Z 3 and Z 4 When both are H, p1+q1+r1+s1 is not 0; A is defined the same as above.

[0326] More specifically, preferred options include: [Chemistry 8] wait, Among them, the preferred option is: [Chemistry 9] .

[0327] As the monomer represented by general formula (1A), A in preferred formula (1A) is -COOM. a The preferred choice is CH2=CFCF2OCF(CF3)COOM. a and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM a (where M is in the formula) a At least one of the groups consisting of (as defined above), more preferably CH2=CFCF2OCF(CF3)COOM a .

[0328] In addition, as a monomer shown in general formula (1), other monomers such as those shown in the following formula can also be cited.

[0329]

[0330] (In the formula, Rf and A are the same as above).

[0331] More specifically, examples include: [Chemistry 10] wait.

[0332] The monomer (I) is also preferably the monomer (2) represented by the general formula (2).

[0333] Polymer (I) is also preferably a polymer (2) comprising a polymer unit (2) based on a monomer shown in general formula (2).

[0334]

[0335] (In the formula, X may be the same or different, and may be -H or F; Y may be -H, -F, alkyl or fluoroalkyl; Rf may be a fluoroalkylene group with 1 to 40 carbon atoms or a fluoroalkylene group with ether or ketone groups with 2 to 100 carbon atoms; A may be the same as above).

[0336] In the manufacturing method disclosed herein, the monomer (2) shown in general formula (2) can be copolymerized with other monomers.

[0337] The polymer (2) can be a homopolymer of the monomers shown in general formula (2) or a copolymer of other monomers.

[0338] In general formula (2), X is -H or F. X can be both -F or at least one -H. For example, one can be -F and the other -H, or both can be -H.

[0339] In general formula (2), Y is -H, -F, alkyl, or fluoroalkyl. An alkyl group is an alkyl group without fluorine atoms, and has 1 or more carbon atoms. The alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. A fluoroalkyl group is an alkyl group containing at least one fluorine atom, and has 1 or more carbon atoms. The fluoroalkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. Y is preferably -H, -F, or CF3, more preferably -F.

[0340] In general formula (2), preferably at least one of X and Y contains a fluorine atom. For example, X can be -H, and Y and Z can be -F.

[0341] In general formula (2), Rf is a fluorinated alkylene group with 1 to 40 carbon atoms, a fluorinated alkylene group with ether bonds having 2 to 100 carbon atoms, or a fluorinated alkylene group with ketone groups having 2 to 100 carbon atoms. It should be noted that the fluorinated alkylene group with ether bonds having 2 to 100 carbon atoms is an alkylene group without oxygen atoms at the end but with ether bonds between carbon atoms.

[0342] The number of carbon atoms in the fluorinated alkylene group of Rf is preferably 2 or more. Furthermore, 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 fluorinated alkylene groups include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, -CF2CF2CF2-, CF2CF2CF2CF2-, etc. The fluorinated alkylene group is preferably a perfluoroalkylene group, more preferably an unbranched, straight-chain perfluoroalkylene group.

[0343] The fluorinated alkylene group having an ether bond preferably has 3 or more carbon atoms. Furthermore, the fluorinated alkylene group having an ether bond preferably has 60 or fewer carbon atoms, more preferably 30 or fewer, even more preferably 12 or fewer, and particularly preferably 5 or fewer. The fluorinated alkylene group having an ether bond is also preferably a divalent group represented by the following general formula. [Chemistry 11]

[0344] (where Z) 1 For F or CF3; Z 2 and Z 3 H or F respectively; Z 4 (where H, F, or CF3 are integers; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0345] Specifically, examples of fluorinated alkylene groups with ether bonds include -CF2CF(CF3)OCF2CF2-, -CF2CF(CF3)OCF2CF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, and -(CF(CF3)CF2-O). n -CF(CF3)- (where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n-CF(CF3)CH2- (where n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorinated alkylene groups with ether bonds mentioned above are preferably perfluoroalkylene groups.

[0346] The fluorinated alkylene group having a ketone group preferably has 3 or more carbon atoms. Furthermore, the fluorinated alkylene group having a ketone group preferably has 60 or fewer carbon atoms, more preferably 30 or fewer, even more preferably 12 or fewer, and particularly preferably 5 or fewer.

[0347] Examples of fluorinated alkylene groups having a ketone group include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, and -CF2CF(CF3)CO-CF2CF2CF2CF2-. The preferred fluorinated alkylene groups having a ketone group are perfluoroalkylene groups.

[0348] Water can also be added to the ketone group in the fluorinated alkylene group. Therefore, monomer (2) can be a hydrate. Examples of fluorinated alkylene groups that have water added to the ketone group include -CF2CF(CF3)C(OH)2-CF2-, -CF2CF(CF3)C(OH)2-CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2-, and -CF2CF(CF3)C(OH)2-CF2CF2CF2CF2-.

[0349] The monomer represented by general formula (2) is preferably selected from at least one of the groups consisting of monomers represented by general formulas (2a), (2b), (2c), (2d), (2e), (2f) and (2g).

[0350]

[0351] (In the formula, n1 represents an integer from 1 to 10, and A is the same as above).

[0352]

[0353] (In the formula, n2 represents an integer from 1 to 5, and A is defined as above).

[0354]

[0355] (where X)1 (This represents F or CF3, where n3 represents an integer from 1 to 10, and A is defined as above).

[0356]

[0357] (In the formula, n4 represents an integer from 1 to 10, n6 represents an integer from 1 to 3, and A and X) 1 Same as the definition above).

[0358]

[0359] (In the formula, n5 represents an integer from 0 to 10, and A and X) 1 Same as the definition above).

[0360]

[0361] (In the formula, n7 represents an integer from 1 to 10, and n8 represents an integer from 1 to 3. A is defined in the same way as above).

[0362]

[0363] (In the formula, n9 represents an integer from 0 to 5, n10 represents an integer from 1 to 8, and n11 represents an integer from 0 to 5. A is defined in the same way as above).

[0364] In general formula (2a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.

[0365] As a monomer represented by the general formula (2a), for example, 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 (where M is in the formula) a Same as the definition above).

[0366] In general formula (2b), from the perspective of the dispersion stability of the obtained composition, n2 is preferably an integer of 3 or less.

[0367] In general formula (2c), from the perspective of water solubility, n3 is preferably an integer of 5 or less, and A is preferably -COOM. a The above M a H, Na, or NH4 are preferred.

[0368] In general formula (2d), from the perspective of the dispersion stability of the composition, X 1 Preferably -CF3, and from the perspective of water solubility, n4 is preferably an integer of 5 or less, and A is preferably -COOM. a M a H, Na, or NH4 are preferred.

[0369] As a monomer represented by the general formula (2d), for example, 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 (where M is in the formula) a (Indicates H, NH4, or alkali metal).

[0370] In general formula (2e), from the perspective of water solubility, n5 is preferably an integer less than or equal to 5, and A is preferably -COOM. a M a H or NH4 is preferred.

[0371] As a monomer represented by the general formula (2e), for example, CF2=CFOCF2CF2CF2COOM can be cited. a (where M is in the formula) a (Indicates H, Na, NH4 or alkali metals).

[0372] In general formula (2f), from the perspective of water solubility, n7 is preferably an integer of 5 or less, and A is preferably -COOM. a Or SO3M a More preferably -COOM a M a The preferred elements are H, Na, K, or NH4.

[0373] As a monomer represented by the general formula (2f), for example, CF2=CF-O-(CF2)3-O-CF2-COOM a (where M is in the formula) a (Indicates H, NH4, or alkali metal).

[0374] In the general formula (2g), from the perspective of water solubility, n9 is preferably an integer of 3 or less, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, and A is preferably -COOM. a Or SO3M a More preferably -COOM a M a The preferred elements are H, Na, K, or NH4.

[0375] As a monomer represented by the general formula (2g), for example, 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 (where M is in the formula) a (Indicates H, NH4, or alkali metal).

[0376] The monomer (I) is also preferably the monomer (3) represented by the general formula (3).

[0377] Polymer (I) is also preferably a polymer (3) comprising a polymer unit (3) based on a monomer shown in general formula (3).

[0378]

[0379] (In the formula, X may be the same or different, and may be -H or F; Y may be -H, -F, alkyl or fluoroalkyl; Rf may be a fluoroalkylene group with 1 to 40 carbon atoms, or a fluoroalkylene group with ether bonds with 2 to 100 carbon atoms. A is the same as above).

[0380] In the manufacturing method disclosed herein, the monomer (3) shown in general formula (3) can be copolymerized with other monomers.

[0381] The polymer (3) can be a homopolymer of the monomers shown in general formula (3) or a copolymer of other monomers.

[0382] It should be noted that fluorinated alkylene groups with 2 to 100 carbon atoms and ether bonds are alkylene groups that do not have oxygen atoms at the end but contain ether bonds between carbon atoms.

[0383] In general formula (3), Rf is preferably a fluorinated alkylene group having 1 to 40 carbon atoms. In general formula (3), preferably at least one of X and Y contains a fluorine atom.

[0384] The monomer represented by general formula (3) is preferably at least one selected from the group consisting of the monomers described below, the monomer represented by general formula (3a),

[0385] (In the formula, n1 represents an integer from 1 to 10, and A is defined as above); and the monomer shown in general formula (3b),

[0386] (In the formula, n2 represents an integer from 1 to 5, and A is defined as above).

[0387] In formulas (3a) and (3b), A is preferably -SO3M. a or COOM a M a Preferably, H, metal atoms, and NR are preferred. 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphatonium with or without substituents. R 2 It represents H or an organic group.

[0388] In general formula (3a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. A is preferably -COOM. a M a H or NH4 is preferred.

[0389] As a monomer represented by the general formula (3a), for example, CF2=CFCF2COOM can be cited. a (where M is in the formula) a Same as the definition above).

[0390] In general formula (3b), from the perspective of the dispersion stability of the obtained composition, n2 is preferably an integer of 3 or less, and A is preferably -COOM. a M a H or NH4 is preferred.

[0391] Next, the preferred configuration for when m in general formula (I) is an integer greater than or equal to 2 will be explained.

[0392] The monomer (I) is preferably selected from at least one of the groups consisting of monomers shown in general formulas (4a) and (4b).

[0393] The polymer (I) is also preferably a polymer (4) comprising a polymer unit (4) based on a monomer selected from the group consisting of monomers shown in general formulas (4a) and (4b).

[0394]

[0395] (where Z) 1 Z 2 A is defined the same as above, Q F1 and Q F2 Whether the groups are the same or different, they are either fluorinated alkylene groups with single bonds or fluorinated oxyalkylene groups with ether bonds between carbon atoms.

[0396] (where Z) 1 Z 2 A, Q F1 and Q F2 Same as the definition above).

[0397] Examples of monomers represented by general formulas (4a) and (4b) include: [Chemistry 12] wait.

[0398] As monomer (I), it is preferably selected from at least one of the group consisting of monomer (1), monomer (2) and monomer (3), more preferably monomer (1), and even more preferably monomer (1A).

[0399] 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).

[0400] In this disclosure, monomer (I) can be copolymerized with other monomers.

[0401] Polymer (I) can be a homopolymer consisting only of polymeric units (I), or a copolymer comprising polymeric units (I) and polymeric units based on other monomers capable of copolymerizing with the monomers shown in general formula (I). From the perspective of solubility in aqueous media, homopolymers consisting only of polymeric units (I) are preferred. The polymeric units (I) may be the same or different in various occurrences, and polymer (I) may contain two or more different polymeric units (I) based on monomers shown in general formula (I).

[0402] As other monomers mentioned above, monomers with the general formula CFR=CR2 (where R is independently H, F, or a perfluoroalkyl group having 1 to 4 carbon atoms) are preferred. Additionally, monomers with fluorinated olefinic bonds having 2 or 3 carbon atoms are preferred. Examples of other monomers 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).

[0403] From the perspective of good copolymerization, it is preferable to select at least one monomer from the group consisting of tetrafluoroethylene (CF2=CF2), trifluorochloroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2), and more preferably at least one monomer from the group consisting of tetrafluoroethylene and vinylidene fluoride. Therefore, the polymerization unit based on the above-mentioned other monomers is preferably a polymerization unit based on tetrafluoroethylene. The polymerization units based on the above-mentioned other monomers may be the same or different in each occurrence, and polymer (I) may contain two or more different polymerization units based on other monomers.

[0404] Other monomers mentioned above can also be represented by the monomers shown in general formula (n1-2). [Chemistry 13]

[0405] (where X) 1 X 2 Same or different, indicated by H or F; X 3 For example, H, F, Cl, CH3 or CF3; X 4 X 5 If they are the same or different, the value is H or F; if a and c are the same or different, the value is 0 or 1; Rf 3 It is a fluorinated alkyl group having 1 to 40 carbon atoms, or a fluorinated alkyl group having ether bonds having 2 to 100 carbon atoms.

[0406] Specifically, a preferred example is 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 (where Rf) 3 (Same as the above formula (n1-2) etc.)

[0407] Other examples of the monomers mentioned above include fluorinated acrylate monomers represented by formula (n2-1). [Chemistry 14]

[0408] (where X) 9 For H, F, or CH3; Rf 4 It is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having ether bonds having 2 to 100 carbon atoms.

[0409] The above Rf 4 Groups that can be listed include: [Chemistry 15]

[0410] (In the formula, d3 is an integer from 1 to 4; e3 is an integer from 1 to 10) etc.

[0411] Other examples of the monomers mentioned above include fluorinated vinyl ethers of formula (n2-2).

[0412] (where Rf) 5 It is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having ether bonds having 2 to 100 carbon atoms.

[0413] Specifically, as a single entity of the general formula (n²-2), examples can be given as follows: [Chemistry 16]

[0414] (In the formula, e6 is an integer from 1 to 10) etc.

[0415] More specifically, examples include: [Chemistry 17] wait.

[0416] In addition, fluorinated allyl ethers represented by the general formula (n2-3) can also be cited.

[0417] (where Rf) 6 Fluorinated alkyl groups having 1 to 40 carbon atoms or fluorinated alkyl groups having ether bonds having 2 to 100 carbon atoms; fluorinated vinyl monomers of general formula (n2-4), etc.

[0418] (where Rf) 7 It is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having ether bonds having 2 to 100 carbon atoms.

[0419] Specifically, as monomers represented by general formulas (n2-3) and (n2-4), examples can be given as follows: [Chemistry 18] Monomers, etc.

[0420] Polymer (I) typically has terminal groups. These terminal groups are those generated during polymerization, and representative terminal groups are independently selected from hydrogen, iodine, bromine, chain-like or branched alkyl groups, and chain-like or branched fluoroalkyl groups, and may optionally contain at least one additional spurious heteroatom. The alkyl or fluoroalkyl groups preferably have 1 to 20 carbon atoms. Generally, these terminal groups are generated by an initiator or chain transfer agent used in the formation of polymer (I), or in a chain transfer reaction.

[0421] In polymer (I), the preferred content of polymeric unit (I) relative to all polymeric units is, in the following order: 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. Particularly preferred is a substantially 100 mol% content of polymeric unit (I), and most preferably, polymer (I) consists solely of polymeric unit (I).

[0422] In polymer (I), the preferred order of content of polymerization units based on monomers capable of copolymerizing with the monomers shown in general formula (I), relative to all polymerization units, is 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. Particularly preferably, the content of polymerization units based on monomers capable of copolymerizing with the monomers shown in general formula (I) is substantially 0 mol%, and polymer (I) most preferably does not contain polymerization units based on other monomers.

[0423] The number-average molecular weight of polymer (I) is preferably 0.1 × 10⁻⁶. 4 The above is preferred to be 0.2×10. 4 The above is further preferably 0.3×10 4 The above is further preferred to be 0.4 × 10⁻⁶. 4 The above, especially the preferred value is 0.5 × 10⁻⁶. 4 The above is particularly preferred, with 1.0 × 10⁻⁶ being the optimal value. 4 The above, especially, is particularly preferred to be 3.0 × 10 4 The optimal value is 3.1 × 10⁻⁶. 4That's all. Additionally, 75.0 × 10 is preferred. 4 The following is more preferably 50.0 × 10 4 The following is a further preferred value: 40.0 × 10 4 Hereinafter, 30.0 × 10 is particularly preferred. 4 The following is particularly preferred: 20.0 × 10 4 The number-average molecular weight and weight-average molecular weight are values ​​calculated using gel permeation chromatography (GPC) with monodisperse polystyrene as a standard. Alternatively, if GPC is not feasible, the number-average molecular weight of polymer (I) can be determined by the correlation between the number-average molecular weight calculated from the number of terminal groups obtained from NMR, FT-IR, etc., and the melt flow rate. The melt flow rate can be determined according to JIS K 7210.

[0424] The preferred order for the weight-average molecular weight of polymer (I) is 0.2 × 10⁻⁶. 4 Above, 0.4×10 4 Above, 0.6×10 4 Above, 0.8×10 4 Above, 1.0×10 4 Above, 2.0×10 4 Above, 5.0×10 4 Above, 10.0×10 4 Above, 15.0×10 4 Above, 20.0×10 4 Above, 25.0×10 4 That's all. Furthermore, regarding the weight-average molecular weight of polymer (I), the preferred order is 150.0 × 10⁻⁶. 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 the following.

[0425] Polymer (I) preferably has an ion exchange rate (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the polymer backbone relative to the ionic group. For the purpose of determining the IXR, precursor groups that become ionic through hydrolysis (e.g., -SO2F) are not considered ionic groups.

[0426] The IXR is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, even more preferably 4 or more, and especially more preferably 5 or more. Furthermore, the IXR is more preferably 43 or less, further preferably 33 or less, and particularly preferably 23 or less.

[0427] The preferred order for the ion exchange capacity of polymer (I) is 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.20 meq / g or more, more than 2.20 meq / g, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, and 3.50 meq / g or more. The ion exchange capacity is the content of ionic groups (anionic groups) in polymer (I), calculated from the composition of polymer (I).

[0428] In polymer (I), ionic groups (anionic groups) are typically distributed along the polymer backbone. The polymer (I) preferably comprises a polymer backbone and repeating side chains bonded to the backbone, and these side chains have ionic groups.

[0429] Polymer (I) preferably contains 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 sulfonates, carboxylates, phosphonates and phosphates.

[0430] The terms "sulfonate, carboxylate, phosphonate, and phosphate" refer to their respective salts or their respective acids capable of forming salts. When using salts, it is preferable that the salt is an alkali metal salt or an ammonium salt. The preferred ionic group is the sulfonate group.

[0431] Polymer (I) is preferably water-soluble. Water solubility refers to the property of easily dissolving or dispersing in an aqueous medium. Polymer (I) that is water-soluble cannot be determined by, for example, dynamic light scattering (DLS) or shows a particle size of less than 5 nm.

[0432] The viscosity of the aqueous solution of polymer (I) is preferably 5.0 mPa·s or more, more preferably 8.0 mPa·s or more, even more preferably 10.0 mPa·s or more, particularly preferably 12.0 mPa·s or more, most preferably 14.0 mPa·s or more, preferably 100.0 mPa·s or less, more preferably 50.0 mPa·s or less, even more preferably 25.0 mPa·s or less, and especially more preferably 20.0 mPa·s or less.

[0433] The viscosity of the aqueous solution of polymer (I) can be determined by adjusting the content of polymer (I) in the aqueous solution to 33% by mass relative to the aqueous solution and measuring the viscosity of the resulting aqueous solution at 20°C using a tuning fork viscometer (model: SV-10) manufactured by A&D Corporation.

[0434] The critical micelle concentration (CMC) of 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, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0435] The critical micelle concentration of polymer (I) can be determined by measuring surface tension. Surface tension can be measured, for example, using a surface tension meter CBVP-A3 manufactured by Kyowa Interface Chemicals Co., Ltd.

[0436] The acid value of polymer (I) is preferably 60 or higher, more preferably 90 or higher, even more preferably 120 or higher, particularly preferably 150 or higher, most preferably 180 or higher, and the upper limit is not particularly limited, but preferably 300 or lower.

[0437] For the acid value of polymer (I), polymer (I) has anionic groups other than acidic functional groups, such as -COOM. a -SO3M a -OSO3M a Or C(CF3)2OM a (M a Metal atoms, NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 In the case of H or organic groups, the determination can be performed by acid-base titration after converting these groups into acidic groups.

[0438] Compound (II) is represented by the general formula (II).

[0439] General Formula (II):

[0440] (in the formula, R FA1 -Rf 1 p -R F -O q -, R FA2 -Rf 2 p -R FX -O q -, R F It is a divalent fluorinated polyether group. R FX It is a divalent fluorinated polyether group containing anionic groups. Rf 1 and Rf2 Each can be independently represented by a C atom that is substituted with one or more fluorine atoms. 1-6 Alkylene p can be 0 or 1 independently. Each q is independently either 0 or 1. X A Each group is independently a single bond or a 2- to 10-valent group. T X and T X Each can be independently selected from (i) C1 to C2 groups containing one or more of H, O, and Cl, and without the aforementioned anionic groups. 24 (i) Hydrogen (fluorine) hydrocarbon group and (ii) C1-C1 groups containing at least one of the above-mentioned anionic groups. 24 (A group composed of (hydrogen)(fluorine) hydrocarbon groups).

[0441] In equation (II), R FA1 -Rf 1 p -R F -O q -

[0442] In equation (II), R FA2 -Rf 2 p -R FX -O q -

[0443] In equation (II), Rf 1 and Rf 2 Each can be independently represented by a C atom that is substituted with one or more fluorine atoms. 1-6 Alkylene.

[0444] The C atoms mentioned above can also be substituted by one or more fluorine atoms. 1-6 The "C" in alkylene 1-6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1-3 Alkylene, more preferably straight-chain C 1-3 Alkylene.

[0445] Rf 1 and Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1-6 Alkylene, more preferably C 1-6 Perfluoroalkylene, more preferably C 1-3 Perfluoroalkylene groups.

[0446] The above C 1-6 Perfluoroalkylene groups can be straight-chain or branched, preferably straight-chain or branched C.1-3 Perfluoroalkylene, more preferably straight-chain C 1-3 Perfluoroalkylene compounds, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0447] In the above formulas, p is independently either 0 or 1. In one case, p is 0. In another case, p is 1.

[0448] In the above formulas, q is independently either 0 or 1. In one mode, q is 0. In another mode, q is 1.

[0449] In equation (II), R F It is a divalent fluorinated polyether group.

[0450] R F Preferably, the group is represented by the following formula.

[0451] [In the formula:] R Fa Each can be independently a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers from 0 to 200, and the sum of a, b, c, d, e, and f is greater than 1. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula. Wherein, in all R... Fa In the case where the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.

[0452] R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom. Wherein, in all R... Fa If the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.

[0453] a, b, c, d, e, and f can each be independently and preferably an integer from 0 to 100, more preferably an integer from 0 to 50.

[0454] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, for example, it can be 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, and even more preferably 60 or less, for example, it can be 50 or less or 30 or less.

[0455] These repeating units can be linear, branched, or contain ring structures. For example, -(OC6F 12)- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)), etc. -(OC5F 10 - can be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(that is, in the above formula, R Fa The fluorine atom can be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- can be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0456] The above-mentioned ring structure can be a ternary ring, a quaternary ring, a quinary ring, or a hexaternary ring.

[0457] [Chemistry 19]

[0458] [In the formula, Indicates the bonding location.

[0459] The aforementioned ring structure can preferably be a four-membered ring, a five-membered ring, or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

[0460] The repeating unit with a ring structure is preferably the following unit.

[0461] [Chemistry 20]

[0462] [In the formula, Indicates the bonding location.

[0463] In one embodiment, the repeating units described above are in a linear chain.

[0464] In one embodiment, the aforementioned repeating unit is branched.

[0465] In one approach, R F It is a group represented by any of the following formulas (f1) to (f6).

[0466]

[0467] [In the formula, d is an integer from 1 to 200, and e is 0 or 1, preferably 0]

[0468] [In the formula, c and d are each independent integers above 0 and below 30, and e and f are each independent integers above 1 and below 200.] The sum of c, d, e, and f is 2 or more. The order of repeating units with c, d, e, or f enclosed in parentheses is arbitrary in the formula.

[0469] [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in, or combinations of two or three groups independently selected from these groups, g is an integer from 2 to 100.

[0470] [In the formula, R] 6 It is either OCF2 or OC2F4. R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups independently selected from these groups, R 6’ It is either OCF2 or OC2F4. R 7’ Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, 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 for: [Chemistry 21]

[0471] (in the formula, [Indicates the bonding location];

[0472] [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, and the order of repeated units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0473] [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d and e are each an integer greater than 0 and less than 200, and the order of the repeated units marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula].

[0474] In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, even more preferably 15 to 50, and for example, an integer from 25 to 35. In the above formula (f1), OC3F6 is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). In one embodiment, e is 0. In another embodiment, e is 1. In the above formula (f1), (OC2F4) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2).

[0475] In the above formula (f2), e and f are each preferably integers from 5 to 200, more preferably from 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f -The group shown. In another embodiment, formula (f2) can be -(OC2F4). e -(OCF2) f - The group shown.

[0476] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R7 Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably OC3F6 or OC4F8. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8; examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, and -OC2F... 4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4-、and-OC4F8OC2F4OC2F4-, etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 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 It can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g -or-(OC2F4-OC4F8) g -

[0477] In the above equation (f4), R 6 R 7 The meaning of 'g' is the same as that in the above formula (f3), and they follow the same pattern. R 6' R 7' and g' are respectively related to R recorded in the above formula (f3). 6 R 7 It has the same meaning as 'g' and follows the same pattern.

[0478] R r Preferred options are: [Chemistry 22]

[0479] [In the formula, [Indicating the bonding position], more preferably: [Chemistry 23]

[0480] [In the formula, Indicates the bonding location.

[0481] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0482] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0483] In one approach, R F The group is represented by the formula (f1) above.

[0484] In one approach, R F The group is shown in the above formula (f2).

[0485] In one approach, R F The group is represented by formula (f3) or (f4) above.

[0486] In one approach, R F The group is represented by the formula (f3) above.

[0487] In one approach, R F The group is represented by the formula (f4) above.

[0488] In one approach, R F The group is represented by the formula (f5) above.

[0489] In one approach, R F The group is represented by the formula (f6) above.

[0490] In R F In this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is preferably 0.1 to 10, more preferably 0.2 to 5, even more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85. By making the e / f ratio 0.1 or higher, the stability of the compound can be further improved. The larger the e / f ratio, the greater the improvement in the stability of the compound.

[0491] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or higher, more preferably 1.0 to 2.0.

[0492] In equation (II), R FX It is a divalent fluorinated polyether group containing anionic groups.

[0493] In addition to anionic groups such as sulfate groups and carboxyl groups, the aforementioned anionic groups also include functional groups that provide anionic groups, such as acid groups like -COOH and acid salt groups like -COONH4. Preferably, the anionic groups are sulfate groups, carboxyl groups, phosphate groups, phosphonate groups, sulfonate groups, or -C(CF3)2OM. a (where M is in the formula) a -H, metal atom, -NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 (H or organic groups).

[0494] R FX The aforementioned fluorinated polyether group can be a group in which one or more hydrogen atoms of the polyether group are replaced by fluorine atoms, preferably a perfluorinated polyether group.

[0495] R FX Preferably, it has a divalent fluorinated polyether group having a repeating unit selected from the group consisting of the following units. (a1)-CF2CF(G x )O- (b1)-CF(G x )O- (c1)-CF2(CF2) x1 CF(G x (CF2) x2 O - (X1 and X2 are zero or integers from 1 to 2, but are conditional on X1 + X2 being at least 1). [here, G x It is a C1-C5 perfluoro(oxy)alkylene group containing at least one anionic group as detailed above.

[0496] It should be noted that the components of R F and R FX The order in which the repeating units exist is arbitrary.

[0497] In the above compound (II), R FA1 and R FA2 The number-average molecular weight of the fraction 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. In this specification, R... FA1 and R FA2 The number average molecular weight is obtained by 19 Values ​​measured by F-NMR.

[0498] In equation (II), X AThis can be understood as the fluorinated polyether portion (R) FA1 and R FA2 ) and the part containing anionic groups (T) X and T X The linking group is connected by '). Therefore, as long as the compound shown in formula (II) can exist stably, then X A It can be a single bond or any group.

[0499] X A Each group is independently a single bond or a group with a valence of 2 to 10.

[0500] X A Each of them is preferably a single bond or an organic group with a 2 to 10 valence.

[0501] In one manner, X A It does not contain siloxane bonds (-Si-O-Si-).

[0502] The above X A The 2- to 10-valent groups are preferably 2- to 8-valent groups. In one embodiment, the 2- to 10-valent groups are preferably 2- to 4-valent groups, more preferably 2-valent groups. In another embodiment, the 2- to 10-valent groups are preferably 3- to 8-valent groups, more preferably 3- to 6-valent groups.

[0503] In one manner, X A It is a single bond or a divalent group.

[0504] 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.

[0505] In one manner, X A It is a trivalent to hexavalent group, preferably a trivalent to hexavalent organic group.

[0506] In one manner, X A It is a trivalent group, preferably a trivalent organic group.

[0507] In one manner, X A It is a single key.

[0508] In another way, X A It is a divalent organic group.

[0509] In one way, as X A Examples include single bonds or divalent organic groups as shown in the following formula.

[0510] [In the formula:] R51 Indicates a single bond, -(CH2) s5 -or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). s5 -, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2. X 51 Represents -(X) 52 ) l5 -, X 52 Each can be independently represented by -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -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 -The groups in the composition R 53 Each independently represents phenyl, C 1-6 Alkyl or C 1-6 Alkoxy, preferably phenyl or C 1-6 Alkyl, more preferably methyl, R 54 Each independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1-6 Alkyl (preferably methyl), Each occurrence of m5 is an integer from 1 to 100, preferably an integer from 1 to 20. In each occurrence, n5 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3. l5 is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably an integer from 1 to 3. p5 is either 0 or 1. q5 is either 0 or 1. Here, at least one of p5 and q5 is 1, and the order of the repeating units marked with p5 or q5 and enclosed in parentheses is arbitrary. Right side and T X and T X 'bonding'. Here, X A (typically X) A The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1-3 Alkyl and C 1-3One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, X A It was not replaced by these groups.

[0511] In the preferred embodiment, the above X A Each independently is -(R) 51 ) p5 -(X 51 ) q5 -R 52 -. R 52 Indicates a single bond, -(CH2) t5 -or o-phenylene, m-phenylene, or p-phenylene, preferably -(CH2). t5 - t5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. Here, R 52 (typically R) 52 The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1-3 Alkyl and C 1-3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, R... 52 It was not replaced by these groups.

[0512] Preferably, the above X A They can be independently: single bond, C 1-20 Alkylene -R 51 -X 53 -R 52 -,or -X 54 -R 5 - [In the formula, R 51 and R 52 Same as the meaning above, X 53 express: -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(R53 )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-phenylene, m-phenylene, or p-phenylene)-Si(R) 53 )2- (where R is in the formula) 53 R 54 m5 has the same meaning as above. u5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. X 54 express: -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-phenylene, m-phenylene, or p-phenylene)-Si(R) 54 )2- (In the formula, each symbol has the same meaning as above).

[0513] More preferably, the above-mentioned X A Each independently is: single bond, C 1-20 Alkylene -(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 meaning as described above.

[0514] More preferably, the above-mentioned X A They can be independently: single bond, C 1-20 Alkylene -(CH2) s5 -X 53 -(CH2) t5 -,or -X 54 -(CH2) t5 - [In the formula, each symbol has the same meaning as described above].

[0515] In the preferred embodiment, the above X A They can be independently: single bond, C 1-20 Alkylene -(CH2) s5 -X 53 -,or -(CH2) s5 -X 53 -(CH2) t5 - [In the formula, X 53 For -O-, -CONR 54 -or-O-CONR 54 -, R 54 Each independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1-6 alkyl, s5 is an integer from 1 to 20. t5 is an integer from 1 to 20.

[0516] In the preferred embodiment, the above X A They can be independently: -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [In the formula, R 54 Each independently represents a hydrogen atom, a phenyl group, or a carbon atom. 1-6 alkyl, s5 is an integer from 1 to 20. t5 is an integer from 1 to 20.

[0517] In one manner, the aforementioned X A Each independently is: single bond, C 1-20 Alkylene -(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 have the same meaning as described above, and v is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3.

[0518] In the above formula, -(C v H 2v- can be a straight chain or a branched chain, for example, it can be -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0519] The above X A Each can be independently selected from fluorine atoms, C 1-3 Alkyl and C 1-3 Fluoroalkyl (preferably C) 1-3 One or more substituents are substituted in the perfluoroalkyl group. In one manner, X A It is not a substitute.

[0520] In one manner, X A They can each be independently designated as -OC 1-6 Groups other than alkylene groups.

[0521] In another way, as X A For example, the following groups can be cited: [Chemistry 24]

[0522] [Chemistry 25]

[0523] [In the formula, R] 41 Each is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C14 group. 1-6 Alkoxy, preferably methyl, D is a group selected from the following groups. -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- (where Ph refers to phenyl), and [Chemistry 26]

[0524] (where R is in the formula) 42 Each independently represents a hydrogen atom and a carbon atom. 1-6 alkyl or C 1-6 The alkoxy group, preferably methyl or methoxy, more preferably methyl, E is -(CH2)n -(n is an integer from 2 to 6), D and R of the molecular backbone FA1 or R FA2 Bonding, E and R Si Bonding.

[0525] As for the above X A Specific examples, such as: single bond, -CH2OCH2-、 -CH2O(CH2)2-、 -CH2O(CH2)3-、 -CH2O(CH2)4-、 -CH2O(CH2)5-、 -CH2O(CH2)6-、 -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -CH2OCF2CHFOCF2-、 -CH2OCF2CHFOCF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-、 -CH2OCH2CF2CF2OCF2-、 -CH2OCH2CF2CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -(CH2)5-、 -(CH2)6-、 -CO-、 -CONH-、 -CONH-CH2-、 -CONH-(CH2)2-、 -CONH-(CH2)3-、 -CONH-(CH2)4-、 -CONH-(CH2)5-、 -CONH-(CH2)6-、 -CON(CH3)-CH2-、 -CON(CH3)-(CH2)2-、 -CON(CH3)-(CH2)3-、 -CON(CH3)-(CH2)4-、 -CON(CH3)-(CH2)5-、 -CON(CH3)-(CH2)6-、 -CON(Ph)-CH2- (where Ph refers to phenyl), -CON(Ph)-(CH2)2- (where Ph refers to phenyl), -CON(Ph)-(CH2)3- (where Ph refers to phenyl), -CON(Ph)-(CH2)4- (where Ph refers to phenyl), -CON(Ph)-(CH2)5- (where Ph refers to phenyl), -CON(Ph)-(CH2)6- (where Ph refers to phenyl), -CONH-(CH2)2NH(CH2)3-、 -CONH-(CH2)6NH(CH2)3-、 -CH2O-CONH-(CH2)3-、 -CH2O-CONH-(CH2)6-、 -S-(CH2)3-、 -(CH2)2S(CH2)3-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20Si(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-、 [Chemistry 27]

[0526] [Chemistry 28] wait.

[0527] In yet another way, X A Each is an independent formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 - The group shown. In the formula, x1, y1 and z1 are each independent integers from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0528] In the above formula, R 16 Each is independently an oxygen atom, a phenylene group, an imidazolyl group, or an -NR group. 18 -(where R is in the formula) 18 (Represents a hydrogen atom or an organic group) or a divalent organic group. R is preferred. 18 It is an oxygen atom or a divalent polar group.

[0529] As for the aforementioned "divalent polar group", there are no particular limitations; examples include -C(O)- and -C(=NR). 19 )- and -C(O)NR 19 -(In these formulas, R) 19(Indicates 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, n-propyl, which may be substituted with one or more fluorine atoms.

[0530] In the above formula, R 17 Each of the atoms is 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 trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0531] It should be noted that, regarding the aforementioned X A The left side of each style and R FA1 or R FA2 Bonding, right side with T X and T X 'bonding'.

[0532] In yet another way, as X A Examples can be given by the following groups: [Chemistry 29]

[0533] [In the formula, R 41 Each is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 Alkoxy, preferably methyl, Each X A In the base, any number of T are R with respect to the molecular backbone. FA1 or R FA2 The following groups are bonded: -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- (where Ph refers to phenyl), or [Chemistry 30]

[0534] [In the formula, R] 42 Each independently represents a hydrogen atom and a carbon atom. 1-6 alkyl or C1-6 The alkoxy group, preferably methyl or methoxy, more preferably methyl, Several other T components are related to the R of the molecular backbone. Si When they exist in a bonded state, the remaining T atoms are independently methyl, phenyl, or C. 1-6 Alkoxy or free radical trapping group or ultraviolet absorbing group].

[0535] There are no particular limitations on free radical scavenging groups as long as they can capture free radicals generated by light irradiation. Examples include residues of benzophenones, benzotriazoles, benzoic acid esters, salicylic acid benzoates, crotonic acid esters, malondiamide esters, organic acrylates, hindered amines, hindered phenols, or triazines.

[0536] There are no particular limitations on ultraviolet absorbing groups as long as they can absorb ultraviolet light. Examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxaloyl aniline, benzoxazinones, and benzoxazoles.

[0537] In preferred embodiments, examples of preferred free radical scavenging groups or ultraviolet absorbing groups include: [Chemistry 31] .

[0538] In this method, X A Each can be an independent group with a valence of 3 to 10.

[0539] In yet another way, as X A Examples can be given by the following groups: [Chemistry 32]

[0540] [In the formula, R] 25 R 26 and R 27 Each is an independent organic group with a valence of 2 to 6. R 25 With at least one R FA1 or R FA2 Bonding, R 26 and R 27 With at least one R Si Bonding.

[0541] In one approach, R 25 For single bond, C 1-20 Alkylene, C 3-20 Cycloalkylene, C 5-20 Aromatic, -R 57 -X 58-R 59 -、-X 58 -R 59 -or-R 57 -X 58 -. The above R 57 and R 59 Each is independently a single bond, C 1-20 Alkylene, C 3-20 Cycloalkyl or C 5-20 Alpha-aryl. The above X 58 It can be -O-, -S-, -CO-, -O-CO-, or -COO-.

[0542] In one approach, R 26 and R 27 Each is independently a hydrocarbon, or has a group having at least one atom selected from N, O, and S at the end or in the main chain of a hydrocarbon, preferably C. 1-6 Alkyl, -R 36 -R 37 -R 36 -、-R 36 -CHR 38 2-etc. Here, R 36 Each is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R 37 It is N, O, or S, preferably N or O. R 38 -R 45 -R 46 -R 45 -、-R 46 -R 45 -or-R 45 -R 46 - Here, R 45 Each is an alkyl group having 1 to 6 carbon atoms. R 46 It can be N, O, or S, with O being the preferred choice.

[0543] In this method, X A Each can be an independent group with a valence of 3 to 10.

[0544] In yet another way, X A The group is represented by the following formula. [Chemistry 33]

[0545] [In the formula, X] a (A single bond or a divalent organic group).

[0546] The above X a It is a single or divalent linker directly bonded to the isocyanuric acid ring. As X aPreferably, it is a single bond, an alkylene group, or a divalent group containing at least one type of bond selected from the group consisting of ether bonds, ester bonds, amide bonds, and thioether bonds; more preferably, it is a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one type of bond selected from the group consisting of ether bonds, ester bonds, amide bonds, and thioether bonds.

[0547] As X a Further preferred groups are those represented by the following formula.

[0548] (where X) 121 ~X 124 Each can be independently H, F, OH or -OSi (OR) 121 )3 (where R is 3) 121 Each is an alkyl group having 1 to 4 carbon atoms. The above X a1 -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 connected to CX) 121 X 122 (bonding), x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.

[0549] As for the above X a1 Preferably -O- or -C(=O)O-.

[0550] As for the above X a The following groups are particularly preferred: The groups shown, (In the formula, m11 is an integer from 1 to 3, m12 is an integer from 1 to 3, and m13 is an integer from 1 to 3); -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 -The group shown, (In the formula, m14 is an integer from 1 to 3, m15 is an integer from 1 to 3, and m16 is an integer from 1 to 3); -(CF2) m17 -(CH2) m18 -The group shown, (In the formula, m17 is an integer from 1 to 3, and m18 is an integer from 1 to 3); -(CF2) m19 -(CH2) m20-O-CH2CH(OSi(OCH3)3)-(CH2) m21 -The group shown, (In the formula, m19 is an integer from 1 to 3, m20 is an integer from 1 to 3, and m21 is an integer from 1 to 3); or -(CH2) m22 -The group shown, (In the formula, m22 is an integer from 1 to 3).

[0551] As for the above X a There are no specific limitations; examples include -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, and -(CF2). n5 -(n5 is an integer from 0 to 4), -(CF2) n5 -(CH2) m5 -(n5 and m5 are each an independent integer from 0 to 4), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2-, etc.

[0552] In this method, X A Each can be a divalent or trivalent group independently.

[0553] In one embodiment, compound (II) of formula (II) does not contain siloxane bonds (-Si-O-Si-).

[0554] Compound (II) is not particularly limited and may have 5 × 10 2 ~1×10 5 The number average molecular weight. Within this range, from the viewpoint of polymerization stability, a number average molecular weight of 2,000 or more, more preferably 2,500 or more, and 32,000 or less, more preferably 12,000 or less, is preferred as the lower limit. It should be noted that the number average molecular weight of compound (II) is determined by... 19 Values ​​measured by F-NMR.

[0555] In one embodiment, the number average molecular weight of compound (II) is preferably 500 or more, more preferably 1,000 or more, further preferably 2,000 or more, even more preferably 3,000 or more, and preferably 30,000 or less, more preferably 20,000 or less, further preferably 15,000 or less, even more preferably 10,000 or less, and particularly preferably 6,000 or less.

[0556] In another embodiment, the number average molecular weight of compound (II) is preferably 4,000 or more, more preferably 5,000 or more, more preferably 6,000 or more, and preferably 30,000 or less, more preferably 10,000 or less.

[0557] As a compound (II), for example, the compound described in International Publication No. 2019 / 048394 can be cited.

[0558] The content of the aforementioned polymeric compound in the TFE-based polymer composition disclosed herein 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, 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 aforementioned TFE-based polymer.

[0559] The content of the above-mentioned polymeric compounds in the TFE-based polymer composition was determined by solid-state NMR.

[0560] In addition, the following publications are cited: International Publication No. 2014 / 099453, International Publication No. 2010 / 075497, International Publication No. 2010 / 075496, International Publication No. 2011 / 008381, International Publication No. 2009 / 055521, International Publication No. 1987 / 007619, Japanese Patent Application Publication No. 61-293476, International Publication No. 2010 / 075494, International Publication No. 2010 / 075359, International Publication No. 2012 / 082454, International Publication No. 2006 / 119224, and International Publication No. 2013 / 085864. Methods for determining the polymers described in various publications, including International Publication Nos. 2012 / 082707, 2012 / 082703, 2012 / 082451, 2006 / 135825, 2004 / 067588, 2009 / 068528, Japanese Patent Application Publication Nos. 2004-075978, 2001-226436, 1992 / 017635, 2014 / 069165, and Hei 11-181009, can be used as methods for determining the content of the aforementioned polymers.

[0561] TFE-based polymer compositions containing polymeric compounds with ionic groups are obtained, for example, by polymerization of the aforementioned polymeric compounds.

[0562] The TFE-based polymer compositions disclosed herein are preferably substantially free of moisture. This suppresses gas generation and deterioration of electrochemical device characteristics. Furthermore, a wide range of electrode active materials and solid electrolytes can be selected, which is advantageous in the manufacturing process. "Substantially free of moisture" means that the moisture content relative to the above-described TFE-based polymer compositions is 0.010% by mass or less.

[0563] The moisture 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.

[0564] The moisture content was determined using the following method.

[0565] The mass of the TFE-based polymer composition before and after heating at 150°C for 2 hours was determined and calculated using the following formula. Three samples were taken, and the mass was calculated for each sample. The average value was then used.

[0566]

[0567] The TFE-based polymer composition disclosed herein can have a 1.0% mass reduction temperature of 492°C or lower.

[0568] A TFE-based polymer composition with a 1.0% mass reduction temperature of 492°C or lower is obtained by using a hydrocarbon-based surfactant. The aforementioned 1.0% mass reduction temperature is a value determined by the following method.

[0569] Approximately 10 mg of a TFE-based polymer composition that has not been heated to temperatures above 300°C is accurately weighed and placed in a dedicated aluminum pan for TG-DTA (differential thermal-thermogravimetric analysis). The 1.0% mass reduction temperature is defined as the temperature at which a 1.0% mass reduction occurs when the aluminum pan is heated at 10°C / min in atmospheric conditions over a temperature range from 25°C to 600°C.

[0570] The thermal stability index (TII) of the TFE-based polymer compositions disclosed herein can be 20 or higher.

[0571] The TFE-based polymer composition with a TII of 20 or more is obtained by using a hydrocarbon-based surfactant. TII is preferably 25 or more, more preferably 30 or more, further preferably 35 or more, and particularly preferably 40 or more. Furthermore, TII is preferably 50 or less.

[0572] The above TII was determined according to ASTM D 4895-89.

[0573] From the perspective of being able to form compound tablets with superior strength, the endothermic peak temperature of the TFE-based polymer composition disclosed herein is 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 addition, it is preferably 350°C or lower, and more preferably 346°C or lower.

[0574] Regarding the aforementioned endothermic peak temperatures, for TFE-based polymer compositions that have not been heated to temperatures above 300°C, differential scanning calorimetry (DSC) was performed at a heating rate of 10°C / min, and the temperature corresponding to the minimum point in the obtained heat of fusion curve was determined. In cases where there are two or more minimum points within a single melting peak, each was used as the endothermic peak temperature.

[0575] From the perspective of being able to form compound tablets with superior strength, the melting point of the TFE-based polymer composition disclosed herein is 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 addition, it is preferably 335°C or lower, more preferably 330°C or lower.

[0576] Regarding the above melting point, differential scanning calorimetry (DSC) was performed on TFE-based polymer compositions that had been heated to temperatures above 300°C at a heating rate of 10°C / min, and the temperature corresponds to the minimum point in the obtained heat of fusion curve.

[0577] From the perspective of being able to form compound tablets with superior strength, the standard specific gravity (SSG) of the TFE-based polymer composition disclosed herein is preferably 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, even more preferably 2.180 or less, and particularly preferably 2.170 or less.

[0578] In addition, the SSG value is preferably 2.130 or higher, but can be 2.140 or higher, or 2.150 or higher.

[0579] The above SSG was measured using samples molded according to ASTM D 4895 89 and determined by the water displacement method according to ASTM D 792.

[0580] The form of the TFE-based polymer composition disclosed herein is not limited, but from the viewpoint of being able to be mixed with electrode active materials and solid electrolytes without using a large amount of dispersion medium, powder is preferred.

[0581] It should be noted that the above-mentioned TFE-based polymer composition can be in a form other than powder, such as a dispersion.

[0582] The TFE-based polymer composition disclosed herein can be suitably manufactured, for example, by a manufacturing method comprising the following steps: a step (A) of preparing an aqueous dispersion of the TFE-based polymer; a step (B) of precipitating the aqueous dispersion to obtain a wetted powder; and a step (C) of drying the wetted powder.

[0583] Step (A) is preferably the following step (A1): obtaining an aqueous dispersion of TFE polymer by emulsion polymerization of TFE in an aqueous medium in the presence of an anionic fluorinated surfactant.

[0584] The emulsion polymerization in step (A1) can be carried out by known methods. For example, in the presence of an anionic fluorinated surfactant and a polymerization initiator, emulsion polymerization of the monomers required to form the above-mentioned TFE-based polymer is carried out in an aqueous medium, thereby obtaining an aqueous dispersion containing particles (primary particles) of the above-mentioned TFE-based polymer. In the above-mentioned emulsion polymerization, chain transfer agents, buffers, pH adjusters, stabilizing agents, dispersion stabilizers, free radical scavengers, etc., may be used as needed.

[0585] The emulsion polymerization described above can, for example, be carried out in an aqueous medium in the presence of anionic fluorinated surfactants and polymerization initiators.

[0586] The emulsion polymerization described above can be carried out as follows: An aqueous medium, the aforementioned anionic fluorinated surfactant, monomers, and other additives as needed are added to a polymerization reactor. The contents of the reactor are stirred, and the reactor is maintained at a specified polymerization temperature. Then, a specified amount of polymerization initiator is added to initiate the polymerization reaction. After the polymerization reaction begins, monomers, polymerization initiators, chain transfer agents, and the aforementioned surfactants can be added as needed, depending on the desired outcome.

[0587] As for the aforementioned polymerization initiator, there are no particular limitations as long as it can generate free radicals within the polymerization temperature range; known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, it can be combined with reducing agents to initiate polymerization in a redox manner. The concentration of the aforementioned polymerization initiator is appropriately determined based on the type of monomer, the molecular weight of the target TFE-based polymer, and the reaction rate.

[0588] Oil-soluble free radical polymerization initiators or water-soluble free radical polymerization initiators can be used as the polymerization initiators mentioned above.

[0589] As an oil-soluble free radical polymerization initiator, it can be a known oil-soluble peroxide, such as the following peroxides as representative substances: diisopropyl peroxide, disec-butyl peroxide, and other dialkyl peroxide esters; tert-butyl peroxide, tert-butyl peroxyisobutyrate, and other peroxide esters; dialkyl peroxides such as di-tert-butyl peroxide; and bis(ω-hydro-dodecylfluoroheptanoyl) peroxide, bis(ω-hydro-tetradecylfluoroheptanoyl) peroxide, bis(ω-hydro-hexadecylfluorononanoyl) peroxide, bis(perfluorobutyryl) peroxide, bis(perfluoropentanoyl) peroxide, bis(perfluorohexanoyl) peroxide, bis(perfluoroheptanoyl) peroxide, bis(perfluorooctanoyl) peroxide, bis(perfluorooctanoyl) peroxide, etc. Oxides, di(perfluorononanoyl) peroxides, di(ω-chloro-hexafluorobutyryl) peroxides, di(ω-chloro-decafluorohexanoyl) peroxides, di(ω-chloro-tetrafluorooctanoyl) peroxides, ω-hydro-dodecanoyl-ω-hydrohexafluorononanoyl-peroxides, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxides, ω-hydro-dodecanoyl-perfluorobutyryl-peroxides, di(dichloropentafluorobutyryl) peroxides, di(trichlorooctafluorohexanoyl) peroxides, di(tetrachloroundecanoyl) peroxides, di(pentachlorotetrafluorodecanoyl) peroxides, di(undecanoyltridodecanoyl)fluoroethoacyl) peroxides, etc., are all di[perfluoro(or fluorochloro)acyl] peroxides; etc.

[0590] As a water-soluble free radical polymerization initiator, it can be a known water-soluble peroxide, such as ammonium salts, potassium salts, sodium salts of persulfate, perboric acid, perchloric acid, superphosphoric acid, and percarbonate, as well as tert-butyl maleate peroxide, tert-butyl hydroperoxide, and bisuccinic acid peroxide. Among these, ammonium persulfate and bisuccinic acid peroxide are preferred. It may also contain reducing agents such as sulfites and sulfites, the amount of which can be 0.1 to 20 times relative to the peroxide.

[0591] There is no particular limitation on the amount of water-soluble free radical polymerization initiator added. It is acceptable to add an amount (e.g., a concentration of several ppm relative to water) that will not significantly reduce the polymerization rate when added once, gradually, or continuously at the beginning of polymerization. The upper limit is the range in which the heat of polymerization can be deheated from the surface of the equipment while increasing the reaction temperature. More preferably, the upper limit is the range in which the heat of polymerization can be removed from the surface of the equipment.

[0592] From the perspective of easily obtaining the above-mentioned physical properties, the amount of polymerization initiator added relative to the aqueous medium is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, and preferably 100 ppm or less, more preferably 10 ppm or less.

[0593] For example, in polymerization at low temperatures below 30°C, a redox initiator composed of an oxidant and a reducing agent is preferred as the polymerization initiator. Examples of oxidants include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, and bromates. Examples of reducing agents include sulfites, bisulfites, bromates, diimides, and oxalic acid. Examples of persulfates include ammonium persulfate and potassium persulfate. Examples of sulfites include sodium sulfite and ammonium sulfite. To improve the decomposition rate of the initiator, it is also preferable to add copper or iron salts to the combination of redox initiators. Examples of copper salts include copper(II) sulfate, and examples of iron salts include ferric(II) sulfate.

[0594] As the above-mentioned redox initiator, the preferred oxidant is permanganic acid or its salt, persulfate, manganese triacetate, cerium(IV) salt, or bromic acid or its salt, and the preferred reducing agent is dicarboxylic acid or its salt, or diimine.

[0595] More preferably, the oxidant is permanganic acid or its salt, persulfate, or bromic acid or its salt, and the reducing agent is dicarboxylic acid or its salt.

[0596] Examples of redox initiators 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.

[0597] When using a redox initiator, either the oxidant or the reducing agent can be added to the polymerization reactor beforehand, followed by the addition of the other continuously or intermittently to initiate polymerization. For example, when using potassium permanganate / oxalic acid, it is preferable to add oxalic acid to the polymerization reactor and then continuously add potassium permanganate thereto.

[0598] It should be noted that when the redox initiator in this specification is described as "potassium permanganate / oxalic acid," it refers to the combination of potassium permanganate and oxalic acid. The same applies to other compounds.

[0599] The aforementioned redox initiator is particularly preferably a combination of an oxidant as a salt and a reducing agent as a salt.

[0600] For example, the oxidizing agent of the above-mentioned salt is more preferably at least one selected from the group consisting of persulfate, permanganate, cerium(IV) salt and bromate, further preferably permanganate, and particularly preferably potassium permanganate.

[0601] Furthermore, the reducing agent for the aforementioned salt is more preferably at least one selected from the group consisting of oxalate, malonate, succinate, glutarate and bromate, and is even more preferably oxalate, particularly preferably ammonium oxalate.

[0602] Specifically, the redox initiator is preferably selected from at least one of 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, it is selected from at least one of 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, it is selected from potassium permanganate / oxalic acid.

[0603] When using a redox initiator, the oxidant and reductant can be added all at once at the beginning of polymerization, or the reductant can be added all at once at the beginning of polymerization and the oxidant can be added continuously, or both the oxidant and reductant can be added continuously.

[0604] When one of the above-mentioned redox polymerization initiators is added at the beginning of polymerization and the remaining one is added continuously, from the perspective of obtaining TFE-based polymers with low SSG, it is preferable to slowly reduce the rate of addition, and even more preferably to stop the addition during polymerization. The preferred time for stopping the addition is before 20% to 40% of the total TFE consumed in the polymerization reaction has been consumed.

[0605] When using a redox initiator as the polymerization initiator, the amount of oxidant added relative to the aqueous medium is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, further preferably 0.5 ppm or more, even more preferably 1 ppm or more, particularly preferably 5 ppm or more, especially more preferably 10 ppm or more, and preferably 10,000 ppm or less, more preferably 1,000 ppm or less, further 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, further 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, further preferably 100 ppm or less, and even more preferably 50 ppm or less.

[0606] Furthermore, when a redox initiator is used in the above-described emulsion polymerization, the polymerization temperature is preferably 100°C or below, more preferably 95°C or below, and even more preferably 90°C or below. Additionally, it is preferably 10°C or above, more preferably 20°C or above, and even more preferably 30°C or above.

[0607] As polymerization initiators, water-soluble free radical polymerization initiators and redox initiators are preferred from the perspective of easily obtaining the aforementioned physical properties.

[0608] The aforementioned aqueous medium refers to the reaction medium that enables polymerization, which is a liquid containing water. There are no particular limitations on the aqueous medium as long as it contains water; it can contain water and non-fluorinated organic solvents such as alcohols, ethers, and ketones, and / or fluorinated organic solvents with a boiling point below 40°C.

[0609] In the above emulsion polymerization, nucleating agents, chain transfer agents, buffers, pH adjusters, stabilizing agents, dispersing stabilizers, free radical scavengers, decomposers of polymerization initiators, dicarboxylic acids, etc., may be used as needed.

[0610] To adjust the particle size, the above emulsion polymerization is preferably carried out by adding a nucleating agent. The nucleating agent is preferably added before the polymerization reaction begins.

[0611] As the nucleating agent mentioned above, a known nucleating agent can be used, preferably at least one selected from the group consisting of fluorinated polyethers, nonionic surfactants and chain transfer agents, more preferably a nonionic surfactant.

[0612] Examples of the aforementioned fluorinated polyethers include perfluoropolyether (PFPE) acids or their salts.

[0613] The aforementioned perfluoropolyether (PFPE) acid or its salts 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. In addition, more than two types of fluorocarbon groups can exist in the molecule.

[0614] A representative structure has repeating units as 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 These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed in that document, the aforementioned PFPE acid or its salt may have a carboxylic acid group or its salt at one or both ends. Additionally, the aforementioned PFPE acid or its salt may have a sulfonic acid group, a phosphonic acid group, or its salt at one or both ends. Furthermore, the aforementioned PFPE acid or its salt may have different groups at each end. Regarding monofunctional PFPE, the other end of the molecule is usually perfluorinated and may also contain a hydrogen or chlorine atom. The aforementioned PFPE acid or its salt has at least two ether oxygen groups, preferably at least four ether oxygen groups, and more preferably at least six ether oxygen groups. Preferably, at least one of the fluorocarbon groups separating the ether oxygen groups has two or three carbon atoms, more preferably at least two of such fluorocarbon groups. More preferably, at least 50% of the fluorocarbon groups separating the ether oxygen groups have two or three carbon atoms. Furthermore, the PFPE acids or their salts preferably have a total of at least 15 carbon atoms; for example, the minimum value of n or n+m in the repeating unit structure is preferably at least 5. Two or more of the PFPE acids or their salts having acid groups at one or both ends can be used in the manufacturing method of this disclosure. The PFPE acids or their salts preferably have a number-average molecular weight of less than 6000 g / mol.

[0615] From the perspective of enabling further high molecular weight increases in TFE-based polymers and improving the strength of the compound tablets, the above-mentioned emulsion polymerization is preferably carried out with the addition of a free radical scavenger or a polymerization initiator decomposer. The free radical scavenger or polymerization initiator decomposer is preferably added after the start of the polymerization reaction, preferably before 10% or more, and preferably 20% or more, of the total TFE consumed in the polymerization reaction is polymerized, and further preferably before 50% or less, and preferably 40% or less, of the polymerized TFE. In the case of depressurization and repressurization as described later, it is preferable to add it afterwards.

[0616] As the aforementioned free radical scavengers, compounds that do not possess the ability to re-initiate after addition or chain transfer into the polymerization system are used. Specifically, compounds with the following functions are used: readily undergoing chain transfer reactions with primary or growth free radicals to generate stable free radicals that do not react with monomers; or readily undergoing addition reactions with primary or growth free radicals to generate stable free radicals.

[0617] The activity of substances commonly referred to as chain transfer agents is characterized by chain transfer constants and re-initiation efficiency. Among chain transfer agents, substances with a re-initiation efficiency of essentially 0% are called free radical scavengers.

[0618] The aforementioned free radical scavengers can also be described as compounds whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant, and whose re-initiation efficiency is substantially zero%. "Substantially zero re-initiation efficiency" means that the generated free radicals make the free radical scavenger a stable free radical.

[0619] Preferably, the compound is a compound with a chain transfer constant (Cs) with TFE at the polymerization temperature (= chain transfer rate constant (kc) / polymerization rate constant (kp)) greater than 0.1. More preferably, the chain transfer constant (Cs) of the above compound is 0.5 or more, further preferably 1.0 or more, even more preferably 5.0 or more, and particularly preferably 10 or more.

[0620] As the aforementioned free radical scavenger, it is preferably selected from at least one of the group consisting of aromatic hydroxyl compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and copper chloride (CuCl2).

[0621] Examples of aromatic hydroxyl compounds include non-substituted phenols, polyphenols, salicylic acid, meta-salicylic acid or para-salicylic acid, gallic acid, naphthol, etc.

[0622] Examples of non-substituted phenols include o-nitrophenol, m-nitrophenol, or p-nitrophenol, o-aminophenol, m-aminophenol, or p-aminophenol, and p-nitrosophenol. Examples of polyphenols include catechol, resorcinol, hydroquinone, pyrogallol, pyrogallol, naphthol, and resorcinol.

[0623] Examples of aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and benzidine.

[0624] Examples of the aforementioned quinone compounds include ortho-benzoquinone, meta-benzoquinone or para-benzoquinone, 1,4-naphthoquinone, alizarin, etc.

[0625] Examples of thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN).

[0626] As the aforementioned free radical scavenger, aromatic hydroxyl compounds are preferred, non-substituted phenols or polyphenols are more preferred, and hydroquinone is even more preferred.

[0627] From the perspective of moderately reducing the standard proportion, the amount of the aforementioned free radical scavenger added is preferably equivalent to 3% to 500% (molar basis) of the polymerization initiator concentration. A more preferred lower limit is 10% (molar basis), and even more preferably 15% (molar basis). A more preferred upper limit is 400% (molar basis), and even more preferably 300% (molar basis).

[0628] As a decomposing agent for the aforementioned polymerization initiator, any compound capable of decomposing the polymerization initiator used is acceptable, and preferably at least one selected from the group consisting of sulfites, bisulfites, bromates, diimides, 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 ferric(II) sulfate.

[0629] From the perspective of appropriately reducing the standard proportion, the amount of the above-mentioned decomposing agent added is preferably equivalent to 3% to 500% (molar basis) of the initiator concentration. More preferably, the lower limit is 10% (molar basis), and even more preferably, 15% (molar basis). More preferably, the upper limit is 400% (molar basis), and even more preferably, 300% (molar basis).

[0630] To reduce the amount of coagulated material generated during polymerization, the emulsion polymerization described above can be carried out in the presence of dicarboxylic acid at a concentration of 5 to 500 ppm relative to the aqueous medium, preferably 10 to 200 ppm. If the dicarboxylic acid concentration is too low relative to the aqueous medium, sufficient effect may not be achieved; if it is too high, chain transfer may occur, resulting in a low molecular weight polymer. The dicarboxylic acid concentration is more preferably 150 ppm or less. The dicarboxylic acid can be added before the start of the polymerization reaction or during polymerization.

[0631] As the dicarboxylic acid mentioned above, a dicarboxylic acid represented by the general formula: HOOCRCOOH (where R represents an alkylene group having 1 to 5 carbon atoms) is preferred, succinic acid, malonic acid, glutaric acid, adipic acid, and pimelic acid are more preferred, and succinic acid is even more preferred.

[0632] In the above emulsion polymerization, the polymerization temperature and polymerization pressure are appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, and the reaction rate. Typically, the polymerization temperature is 5°C to 150°C, preferably 10°C or higher, more preferably 30°C or higher, and even more preferably 50°C or higher. Furthermore, it is more preferably 120°C or lower, and even more preferably 100°C or lower.

[0633] The polymerization pressure is 0.05 to 10 MPaG. More preferably, the polymerization pressure is 0.3 MPaG or more, and even more preferably, 0.5 MPaG or more. Furthermore, more preferably, it is 5.0 MPaG or less, and even more preferably, 3.0 MPaG or less.

[0634] When using VDF as the modifying monomer, in the above-described emulsion polymerization, from the perspective of easily obtaining the aforementioned physical properties, it is preferable to set the VDF concentration in the gas in the reactor at the start of polymerization (when the initiator is added) to be 0.001 mol% or more, more preferably 0.01 mol% or more. Furthermore, the above concentration can be 15 mol% or less, preferably 6.0 mol% or less, more preferably 5.0 mol% or less, even more preferably 3.0 mol% or less, and particularly preferably 1.0 mol% or less. The above-described VDF concentration can be maintained thereafter until the polymerization reaction is complete, or pressure can be released midway. It is preferable that VDF is added all at once before the start of polymerization, but it can also be added continuously or intermittently after the start of polymerization.

[0635] When using VDF as a modifying monomer, in the above emulsion polymerization, it is preferable not to depressurize after adding VDF to the polymerization vessel until the polymerization is complete. This allows VDF to remain in the system until the polymerization is finished, further improving the strength of the compound sheets using the obtained TFE-based polymer.

[0636] When using HFP as a modifying monomer, in the above-mentioned emulsion polymerization, from the perspective of easily obtaining the aforementioned physical properties, it is preferable to set the HFP concentration in the reactor gas at the start of polymerization (when the initiator is added) to be 0.01 to 3.0 mol%. Furthermore, the HFP concentration in the reactor gas at the moment when 40% by mass of all TFE consumed in the polymerization reaction is polymerized is preferably greater than 0 mol% and less than 0.2 mol%. This HFP concentration is preferably maintained thereafter until the end of the polymerization reaction. HFP can be added all at once before the start of polymerization, or a portion can be added before the start of polymerization and then added continuously or intermittently after the start of polymerization. By leaving HFP until the end of the polymerization reaction, although the strength of the resulting TFE-based polymer-based compound sheet is high, the extrusion pressure is reduced.

[0637] When using HFP as a modified monomer, in the above emulsion polymerization, from the perspective of further improving the strength of the compound tablet using the obtained TFE-based polymer, it is preferable to depressurize before 5 to 40% by mass of all TFE consumed in the polymerization reaction is polymerized, and then repressurize only through TFE.

[0638] The aforementioned pressure relief is preferably carried out when the pressure inside the reactor is 0.2 MPaG or less, more preferably 0.1 MPaG or less, and even more preferably 0.05 MPaG or less. Furthermore, it is preferable to achieve a pressure of 0.0 MPaG or more.

[0639] Furthermore, the above-mentioned depressurization and repressurization can be performed multiple times. Depressurization can be achieved using a vacuum pump to reduce the pressure.

[0640] When using CTFE as a modifying monomer, in the above-described emulsion polymerization, from the perspective of easily obtaining the aforementioned physical properties, it is preferable to set the CTFE concentration in the gas in the reactor at the start of polymerization (when the initiator is added) to be 0.001 mol% or more, more preferably 0.01 mol% or more. Furthermore, the above concentration is preferably 3.0 mol% or less, more preferably 1.0 mol% or less. The above-mentioned CTFE concentration can be maintained thereafter until the polymerization reaction ends, or pressure can be released midway. CTFE is preferably added all at once before the start of polymerization, or it can be added continuously or intermittently after the start of polymerization.

[0641] When using CTFE as a modifying monomer, in the above emulsion polymerization, it is preferable not to depressurize after adding CTFE to the polymerization vessel until the polymerization is complete. This allows CTFE to remain in the system until the polymerization is finished, further improving the strength of the compound tablets using the obtained TFE-based polymer.

[0642] In addition, step (A) is preferably step (A2) in which TFE is emulsion polymerized in an aqueous medium in the presence of a hydrocarbon surfactant to obtain an aqueous dispersion of TFE polymer.

[0643] In hydrocarbon-based surfactants, the proportion of hydrogen atoms bonded to carbon atoms that are replaced by fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0644] Step (A2) preferably includes the following steps: emulsion polymerization of tetrafluoroethylene alone in an aqueous medium in the presence of a specific hydrocarbon surfactant, or emulsion polymerization of tetrafluoroethylene and a modified monomer capable of copolymerizing with the aforementioned tetrafluoroethylene, and a step of continuously adding the specific hydrocarbon surfactant in the aforementioned steps.

[0645] Continuous addition of a specific hydrocarbon surfactant refers to the addition of the specific hydrocarbon surfactant not all at once, but over a period of time without interruption or in batches. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), or a hydrocarbon surfactant obtained by free radical treatment or oxidation treatment of a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). The aforementioned free radical treatment is any treatment that causes the hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group) to generate free radicals. For example, it can be the following treatment: adding deionized water and the hydrocarbon surfactant to a reactor, sealing the reactor, purging the system with nitrogen, heating and pressurizing the reactor, adding a polymerization initiator, stirring for a certain period, depressurizing until the reactor reaches atmospheric pressure, and then cooling. The aforementioned oxidation treatment is the treatment of adding an oxidant to a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). Examples of oxidizing agents include oxygen, ozone, hydrogen peroxide, manganese oxide (IV), potassium permanganate, potassium dichromate, nitric acid, and sulfur dioxide. Using the above manufacturing method, TFE-based polymers with the same molecular weight as those produced using existing fluorinated surfactants can be manufactured even without the use of existing fluorinated surfactants.

[0646] In the above manufacturing method, the step of continuously adding the specific hydrocarbon surfactant preferably begins when the solid content of the TFE-based polymer formed in the aqueous medium is less than 0.60% by mass. More preferably, the specific hydrocarbon surfactant is added when the solid content is 0.5% by mass or less. More preferably, the specific hydrocarbon surfactant is added when the solid content is 0.3% by mass or less, even more preferably when it is 0.2% by mass or less, and even more preferably when it is 0.1% by mass or less. Particularly preferably, the addition begins simultaneously with the start of polymerization. The solid content refers to the concentration relative to the total concentration of the aqueous medium and the TFE-based polymer.

[0647] In the above-described process of continuously adding a specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant added relative to 100% by mass of the aqueous medium is preferably 0.01 to 10% by mass. More preferably, the lower limit is 0.05% by mass, and even more preferably, the lower limit is 0.1% by mass. More preferably, the upper limit is 5% by mass, and even more preferably, the upper limit is 1% by mass.

[0648] In the process of emulsion polymerization of tetrafluoroethylene alone, or emulsion polymerization of tetrafluoroethylene and a modified monomer capable of copolymerizing with the aforementioned specific hydrocarbon surfactant in an aqueous medium, the amount of the aforementioned specific hydrocarbon surfactant is preferably high, 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. When the amount is less than 0.0001% by mass, the dispersing force may be insufficient; when the amount is greater than 10% by mass, while the effect is proportional to the amount, it may instead cause a decrease in polymerization rate or cessation of the reaction. The amount of the aforementioned specific hydrocarbon surfactant is appropriately determined based on the type of monomer used, the molecular weight of the target TFE-based polymer, etc.

[0649] As the aforementioned specific hydrocarbon-based surfactant, the preferred surfactant is the surfactant represented by the formula RX (where R is a non-fluorinated organic group having 1 to 2000 carbon atoms having one or more carbonyl groups (excluding the carbonyl groups in the carboxyl groups), and X is -OSO3X). 1 -COOX 1 or -SO3X 1 (X 1 For H, metal atoms, NR 1 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 1 R is H or an organic group (preferably a fluorine-free organic group, which may be the same or different). R preferably has 500 or less carbon atoms, more preferably 100 or less, further preferably 50 or less, and even more preferably 30 or less.

[0650] As the specific hydrocarbon-based surfactant mentioned above, at least one surfactant selected from the group consisting of the surfactants described below, specifically surfactant (a) represented by formula (a) below, is preferred. [Chemistry 34]

[0651] (where R is in the formula) 1a It is a straight-chain or branched alkyl group with 1 or more carbon atoms, or a cyclic alkyl group with 3 or more carbon atoms. The hydrogen atoms bonded to the carbon atoms can be replaced by hydroxyl groups or monovalent organic groups containing ester bonds (preferably non-fluorine organic groups). If it has 2 or more carbon atoms, it can contain a carbonyl group. If it has 3 or more carbon atoms, it can contain monovalent or divalent heterocycles, or it can form a ring. R 2a and R 3a Independently a single bond or a divalent linker. R 1a R 2a and R 3a The total number of carbon atoms is 6 or more. X aFor H, metal atoms, NR 4a 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 4a It can be H or an organic group (preferably a fluorine-free organic group), and can be the same or different. R 1a R 2a and R 3a Any two of them can bond together to form a ring; The surfactant (b) shown in formula (b) below, [Chemistry 35]

[0652] (where R is in the formula) 1b It is a straight-chain or branched alkyl group with or without substituents, having 1 or more carbon atoms, or a cyclic alkyl group with or without substituents, having 3 or more carbon atoms. When it has 3 or more carbon atoms, it may contain monovalent or divalent heterocycles, or it may form a ring. R 2b and R 4b Independently, it can be H or a substituent. R 3b It is an alkylene group with 1 to 10 carbon atoms, with or without substituents. n is an integer greater than or equal to 1. p and q are independently integers greater than or equal to 0. X b For H, metal atoms, NR 5b 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5b R can be H or an organic group (preferably a fluorine-free organic group), and can be the same or different. 1b R 2b R 3b and R 4b Any two bonds in the group can bond together to form a ring. L is a single bond, -CO2-B- -OCO-B- -CONR 6b -B- -NR 6b CO-B- Or -CO- (where -CO2-B-, -OCO-B-, -CONR) 6b -B-、-NR 6 (excluding the carbonyl group contained in CO-B-), B is a single bond or an alkylene group with or without substituents, having 1 to 10 carbon atoms, R 6b It is H or an alkyl group with or without substituents, having 1 to 4 carbon atoms. This refers to -OSO3X in the formula. b (The bonded side); The surfactant (c) shown in the following formula (c) [Chemistry 36]

[0653] (where R is in the formula) 1c It is a straight-chain or branched alkyl group with 1 or more carbon atoms, or a cyclic alkyl group with 3 or more carbon atoms. The hydrogen atoms bonded to the carbon atoms can be replaced by hydroxyl groups or monovalent organic groups containing ester bonds (preferably non-fluorine organic groups). If it has 2 or more carbon atoms, it can contain a carbonyl group. If it has 3 or more carbon atoms, it can contain monovalent or divalent heterocycles, or it can form a ring. R 2c and R 3c Independently a single bond or a divalent linker. R 1c R 2c and R 3c The total number of carbon atoms is 5 or more. A c For -COOX c or -SO3X c (X c For H, metal atoms, NR 4c 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 4c R is an H group or an organic group (preferably a fluorine-free organic group, which can be the same or different). 1c R 2c and R 3c Any two of them can bond together to form a ring; The surfactant (d) shown in the following formula (d) [Chemistry 37]

[0654] (where R is in the formula) 1d It is a straight-chain or branched alkyl group with or without substituents, having 1 or more carbon atoms, or a cyclic alkyl group with or without substituents, having 3 or more carbon atoms. When it has 3 or more carbon atoms, it may contain monovalent or divalent heterocycles, or it may form a ring. R 2d and R 4d Independently, it can be H or a substituent. R 3d It is an alkylene group with 1 to 10 carbon atoms, with or without substituents. n is an integer greater than or equal to 1. p and q are independently integers greater than or equal to 0. A d -SO3X d or -COOX d (X d For H, metal atoms, NR 5d4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5d R is an H group or an organic group (preferably a fluorine-free organic group, which can be the same or different). 1d R 2d R 3d and R 4d Any two bonds in the group can bond together to form a ring. L is a single bond, -CO2-B- -OCO-B- -CONR 6d -B- -NR 6d CO-B- Or -CO- (where -CO2-B-, -OCO-B-, -CONR) 6d -B-、-NR 6d (excluding the carbonyl group contained in CO-B-), B is a single bond or an alkylene group with or without substituents, having 1 to 10 carbon atoms, R 6d It is H or an alkyl group with or without substituents, having 1 to 4 carbon atoms. This refers to A in the formula. d (the bonded side); and

[0655] The surfactant (e) shown in the following formula (e) [Chemistry 38]

[0656] (where R is in the formula) 1e ~R 5e Represents H or a monovalent substituent, where R 1e and R 3e At least one of the general formulas in the formula is: -Y e -R 6e The groups shown, R 2e and R 5e At least one of the following represents the general formula: -X e -A e The indicated group, or general formula: -Y e -R 6e The group shown.

[0657] Additionally, X e The presence of the same or different elements in different instances indicates a divalent linking group or bond; A e The same or different occurrences indicate -COOM e -SO3M e or -OSO3M e (M eFor H, metal atoms, NR 7e 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7e It is an H group or an organic group (preferably a fluorine-free organic group); Y e The fact that they appear the same or different indicates that the choice is free from -S(=O)2-, -O-, -COO-, -OCO-, -CONR. 8e -and-NR 8e The divalent linking group or bond in the CO- group, R 8e Indicates H or an organic group (preferably a fluorine-free organic group); R 6e The same or different in each occurrence indicates that at least one alkyl group with two or more carbon atoms selected from the group consisting of carbonyl, ester, amide and sulfonyl groups may be included between carbon atoms; R 1e ~R 5e Any two of them can bond together to form a ring.

[0658] The surfactant (a) is described.

[0659] In equation (a), R 1a It is a straight-chain or branched alkyl group with 1 or more carbon atoms, or a cyclic alkyl group with 3 or more carbon atoms.

[0660] When the alkyl group has 3 or more carbon atoms, a carbonyl group (-C(=O)-) may be included between two carbon atoms. Alternatively, when the alkyl group has 2 or more carbon atoms, the carbonyl group may be included at the end of the alkyl group. That is, acyl groups such as the acetyl group represented by CH3-C(=O)- are also included in the alkyl group.

[0661] Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain monovalent or divalent heterocycles, and may even form a ring. As the heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred; examples include furan rings. 1a In this context, a divalent heterocycle can be inserted between two carbon atoms, or it can be located at the end and bonded to -C(=O)-. A monovalent heterocycle can be located at the end of the aforementioned alkyl group.

[0662] It should be noted that, in this specification, the "number of carbon atoms" of the aforementioned alkyl groups also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the aforementioned heterocycles. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0663] In the aforementioned alkyl group, the hydrogen atom bonded to the carbon atom can be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a non-fluorinated organic group), and preferably not by any functional group.

[0664] As a monovalent organic group containing an ester bond, the following formula can be cited: -OC(=O)-R 101a (where R is in the formula) 101a (A group represented by an alkyl group).

[0665] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0666] In the formula, R 2a and R 3a Independently a single bond or a divalent linker.

[0667] R 2a and R 3a Preferably, it is a single bond, or a straight-chain or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0668] Composition of R 2a and R 3a The aforementioned alkylene groups preferably do not contain carbonyl groups.

[0669] In the aforementioned alkylene groups, the hydrogen atoms bonded to the carbon atoms can be substituted by functional groups, such as hydroxyl groups (-OH) or monovalent organic groups containing ester bonds (preferably fluorine-free organic groups), and preferably not substituted by any functional groups.

[0670] As a monovalent organic group containing an ester bond, the following formula can be cited: -OC(=O)-R 102a (where R is in the formula) 102a (A group represented by an alkyl group).

[0671] In the aforementioned alkylene groups, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkylene groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0672] R 1a R 2a and R 3a The total number of carbon atoms is 6 or more. Preferably, the total number of carbon atoms is 8 or more, more preferably 9 or more, even more preferably 10 or more, more preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less.

[0673] R 1a R 2a and R 3a Any two of them can bond together to form a ring.

[0674] In equation (a), X a For H, metal atoms, NR 4a 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 4a It is an H or an organic group (preferably a fluorine-free organic group). 4 R 4a They can be the same or different. As R... 4a The organic group in R is preferably alkyl. 4a Preferably, the metal atom is 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 mentioned above include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0675] As X a H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR are preferred. 4a 4. From the perspective of easy solubility in water, H, Na, K, Li or NH4 are more preferred; from the perspective of even easier solubility in water, Na, K or NH4 are further preferred; Na or NH4 are particularly preferred; and from the perspective of easy removal, NH4 is the most preferred. a When the surfactant is NH4, it exhibits excellent solubility in aqueous media and is unlikely to leave metal residues in TFE-based polymers or final products.

[0676] As R 1aPreferably, it is a straight-chain or branched alkyl group with 1 to 8 carbon atoms that does not contain a carbonyl group, a cyclic alkyl group with 3 to 8 carbon atoms that does not contain a carbonyl group, a straight-chain or branched alkyl group with 2 to 45 carbon atoms that contains 1 to 10 carbonyl groups, a cyclic alkyl group with 3 to 45 carbon atoms that contains a carbonyl group, or an alkyl group with 3 to 45 carbon atoms containing a monovalent or divalent heterocycle.

[0677] As a surfactant (a), the following surfactants can be exemplified. In each formula, X a As stated above.

[0678] [Chemistry 39]

[0679] [Chemistry 40]

[0680] [Chemistry 41]

[0681] [Chemistry 42]

[0682] [Chemistry 43]

[0683] [Chemistry 44]

[0684] [Chemistry 45]

[0685] [Chemistry 46]

[0686] Surfactant (a) can be manufactured, for example, by the manufacturing method described in International Publication No. 2020 / 022355.

[0687] Next, surfactant (b) will be described.

[0688] In equation (b), R 1b It is a straight-chain or branched alkyl group with or without substituents having 1 or more carbon atoms, or a cyclic alkyl group with or without substituents having 3 or more carbon atoms.

[0689] When the alkyl group has 3 or more carbon atoms, it may also contain monovalent or divalent heterocycles, and may even form a ring. As the heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred; examples include furan rings. 1bIn this context, a divalent heterocycle can be inserted between two carbon atoms, or it can be located at the end and bonded to -C(=O)-. A monovalent heterocycle can be located at the end of the aforementioned alkyl group.

[0690] It should be noted that, in this specification, the “number of carbon atoms” of the aforementioned alkyl group also includes the number of carbon atoms constituting the aforementioned heterocycle.

[0691] Regarding R 1b The alkyl group may have the above-mentioned substituents, preferably halogen atoms, straight-chain or branched alkyl groups with 1 to 10 carbon atoms or cyclic alkyl groups with 3 to 10 carbon atoms, hydroxyl groups, and particularly preferably methyl or ethyl groups.

[0692] As R 1b The alkyl group mentioned above preferably does not contain a carbonyl group.

[0693] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0694] The alkyl group described above preferably does not have any substituents.

[0695] As R 1b Preferably, it is a straight-chain or branched alkyl group with or without substituents, having 1 to 10 carbon atoms, or a cyclic alkyl group with or without substituents, having 3 to 10 carbon atoms. More preferably, it is a straight-chain or branched alkyl group without carbonyls, having 1 to 10 carbon atoms, or a cyclic alkyl group without carbonyls, having 3 to 10 carbon atoms. Even more preferably, it is a straight-chain or branched alkyl group without substituents, having 1 to 3 carbon atoms. Particularly preferred are methyl (-CH3) or ethyl (-C2H5), and most preferably methyl (-CH3).

[0696] In equation (b), R 2b and R 4b Independently H or substituent. Two or more Rs 2b and R 4b They can be the same or different.

[0697] For R 2b and R 4b The above-mentioned substituents are preferably halogen atoms, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, with methyl and ethyl groups being particularly preferred.

[0698] As R 2b and R 4bThe alkyl group mentioned above preferably does not contain a carbonyl group.

[0699] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0700] The alkyl group described above preferably does not have any substituents.

[0701] For R 2b and R 4b The alkyl group described above is preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group, or a cyclic alkyl group with 3 to 10 carbon atoms that does not contain a carbonyl group. More preferably, it is a straight-chain or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a straight-chain or branched alkyl group with 1 to 3 carbon atoms that does not have a substituent. Methyl (-CH3) or ethyl (-C2H5) is particularly preferred.

[0702] As R 2b and R 4b H or a straight-chain or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group is preferred, H or a straight-chain or branched alkyl group with 1 to 3 carbon atoms that does not have a substituent is more preferred, H, methyl (-CH3) or ethyl (-C2H5) is even more preferred, and H is particularly preferred.

[0703] In equation (b), R 3b It is an alkylene group with 1 to 10 carbon atoms, with or without substituents. R 3b When there are more than two, they can be the same or different.

[0704] The aforementioned alkylene groups preferably do not contain carbonyl groups.

[0705] In the aforementioned alkylene groups, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0706] The aforementioned alkylene groups preferably do not have any substituents.

[0707] As the aforementioned alkylene groups, preferably straight-chain or branched alkylene groups with or without substituents having 1 to 10 carbon atoms, or cyclic alkylene groups with or without substituents having 3 to 10 carbon atoms, preferably straight-chain or branched alkylene groups without carbonyls having 1 to 10 carbon atoms, or cyclic alkylene groups without carbonyls having 3 to 10 carbon atoms, more preferably straight-chain or branched alkylene groups without substituents having 1 to 10 carbon atoms, and even more preferably methylene (-CH2-), ethylene (-C2H4-), isopropylene (-CH(CH3)CH2-), or propylene (-C3H6-).

[0708] R 1b R 2b R 3b and R 4b Any two of them can bond together to form a ring, but preferably they do not form a ring.

[0709] In formula (b), n is an integer of 1 or more. Preferably, n is an integer from 1 to 40, more preferably an integer from 1 to 30, even more preferably an integer from 5 to 25, and particularly preferably an integer from 5 to 9 or 11 to 25.

[0710] In equation (b), p and q are independently integers greater than or equal to 0. p is preferably an integer from 0 to 10, more preferably 0 or 1. q is preferably an integer from 0 to 10, more preferably an integer from 0 to 5.

[0711] The sum of n, p, and q is preferably an integer of 5 or more. More preferably, the sum of n, p, and q is an integer of 8 or more. Furthermore, the sum of n, p, and q is 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.

[0712] In equation (b), X b For H, metal atoms, NR 5b 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5b It is an H or an organic group (preferably a fluorine-free organic group). 4 Rs 5b They can be the same or different. As R... 5b The organic group in R is preferably alkyl. 5b Preferably, the metal atom is H or an organic group having 1 to 10 carbon atoms; more preferably, it is H or an organic group having 1 to 4 carbon atoms; and even more preferably, it is 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), with Na, K, or Li being preferred. b It can be a metal atom or NR 5b 4(R 5b (As mentioned above).

[0713] As X b H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR are preferred. 5b 4. From the perspective of easy solubility in water, H, Na, K, Li or NH4 are more preferred; from the perspective of even easier solubility in water, Na, K or NH4 are further preferred; Na or NH4 are particularly preferred; and from the perspective of easy removal, NH4 is the most preferred. b When the surfactant is NH4, it exhibits excellent solubility in aqueous media and is unlikely to leave metal residues in TFE-based polymers or final products.

[0714] In equation (b), L is a single bond, -CO2-B- -OCO-B- -CONR 6b -B- -NR 6b CO-B- Or -CO- (where -CO2-B-, -OCO-B-, -CONR) 6b -B-、-NR 6b (excluding the carbonyl group contained in CO-B-), B is a single bond or an alkylene group with or without substituents, having 1 to 10 carbon atoms, R 6b It is H or an alkyl group with or without substituents, having 1 to 4 carbon atoms. Preferably, the alkylene group has 1 to 5 carbon atoms. Furthermore, preferably, the R group... 6b It is H or methyl. This refers to -OSO3X in the formula. b The bonded side.

[0715] Ideally, L should be a single bond.

[0716] As surfactant (b), compounds represented by the following formula are preferred. [Chemistry 47]

[0717] (where R is in the formula) 1b R 2b L, n and X b (As mentioned above).

[0718] Examples of surfactants (b) include: CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2OSO3Naぁ (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (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)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Naぁ CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Naぁ CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, etc.

[0719] Surfactant (b) can be manufactured by, for example, the manufacturing method described in International Publication No. 2020 / 022355.

[0720] Next, the surfactant (c) will be described.

[0721] In equation (c), R 1c It is a straight-chain or branched alkyl group with 1 or more carbon atoms, or a cyclic alkyl group with 3 or more carbon atoms.

[0722] When the alkyl group has 3 or more carbon atoms, a carbonyl group (-C(=O)-) may be included between two carbon atoms. Alternatively, when the alkyl group has 2 or more carbon atoms, the carbonyl group may be included at the end of the alkyl group. That is, acyl groups such as the acetyl group represented by CH3-C(=O)- are also included in the alkyl group.

[0723] Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain monovalent or divalent heterocycles, and may even form a ring. As the heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred; examples include furan rings.1c In this context, a divalent heterocycle can be inserted between two carbon atoms, or it can be located at the end and bonded to -C(=O)-. A monovalent heterocycle can also be located at the end of the aforementioned alkyl group.

[0724] It should be noted that, in this specification, the "number of carbon atoms" of the aforementioned alkyl groups includes both the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the aforementioned heterocycles. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0725] In the aforementioned alkyl group, the hydrogen atom bonded to the carbon atom can be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a non-fluorinated organic group), and preferably not by any functional group.

[0726] As a monovalent organic group containing an ester bond, the following formula can be cited: -OC(=O)-R 101c (where R is in the formula) 101c (A group represented by an alkyl group).

[0727] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0728] In equation (c), R 2c and R 3c Independently a single bond or a divalent linker.

[0729] R 2c and R 3c Independently preferred are single bonds or straight-chain or branched alkylene groups with 1 or more carbon atoms, or cyclic alkylene groups with 3 or more carbon atoms.

[0730] Composition of R 2c and R 3c The aforementioned alkylene groups preferably do not contain carbonyl groups.

[0731] In the aforementioned alkylene groups, the hydrogen atoms bonded to the carbon atoms can be substituted by functional groups, such as hydroxyl groups (-OH) or monovalent organic groups containing ester bonds (preferably fluorine-free organic groups), and preferably not substituted by any functional groups.

[0732] As a monovalent organic group containing an ester bond, the following formula can be cited: -OC(=O)-R 102c (where R is in the formula) 102c(A group represented by an alkyl group).

[0733] In the aforementioned alkylene groups, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkylene groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0734] R 1c R 2c and R 3c The total number of carbon atoms is 5 or more. Preferably, the total number of carbon atoms is 7 or more, more preferably 9 or more, more preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less.

[0735] R 1c R 2c and R 3c Any two of them can bond together to form a ring.

[0736] In equation (c), A c For -COOX c or -SO3X c (X c For H, metal atoms, NR 4c 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 4c It can be H or an organic group (preferably a fluorine-free organic group, which can be the same or different). As R 4c The organic group in R is preferably alkyl. 4c Preferably, the metal atom is H or an organic group having 1 to 10 carbon atoms; more preferably, it is H or an organic group having 1 to 4 carbon atoms; and even more preferably, it is H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom mentioned above include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0737] As X c H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR are preferred. 4c 4. From the perspective of easy solubility in water, H, Na, K, Li or NH4 are more preferred; from the perspective of even easier solubility in water, Na, K or NH4 are further preferred; Na or NH4 are particularly preferred; and from the perspective of easy removal, NH4 is the most preferred. c When the surfactant is NH4, it exhibits excellent solubility in aqueous media and is unlikely to leave metal residues in TFE-based polymers or final products.

[0738] As R 1cPreferably, it is a straight-chain or branched alkyl group with 1 to 8 carbon atoms that does not contain a carbonyl group, a cyclic alkyl group with 3 to 8 carbon atoms that does not contain a carbonyl group, a straight-chain or branched alkyl group with 2 to 45 carbon atoms that contains 1 to 10 carbonyl groups, a cyclic alkyl group with 3 to 45 carbon atoms that contains a carbonyl group, or an alkyl group with 3 to 45 carbon atoms containing a monovalent or divalent heterocycle.

[0739] As the surfactant (c) mentioned above, the following surfactants can be exemplified. In each formula, A c As stated above.

[0740] [Chemistry 48]

[0741] [Chemistry 49]

[0742] [Transformation 50]

[0743] [Chemistry 51]

[0744] [Chemistry 52]

[0745] [Chemistry 53]

[0746] [Chemistry 54]

[0747] [Chemistry 55]

[0748] Surfactant (c) can be manufactured by, for example, the manufacturing method described in International Publication No. 2020 / 022355.

[0749] Next, the surfactant (d) will be explained.

[0750] In equation (d), R 1d It is a straight-chain or branched alkyl group with or without substituents having 1 or more carbon atoms, or a cyclic alkyl group with or without substituents having 3 or more carbon atoms.

[0751] When the alkyl group has 3 or more carbon atoms, it may also contain monovalent or divalent heterocycles, and may even form a ring. As the heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred; examples include furan rings. 1dIn this context, a divalent heterocycle can be inserted between two carbon atoms, or it can be located at the end and bonded to -C(=O)-. A monovalent heterocycle can also be located at the end of the aforementioned alkyl group.

[0752] It should be noted that, in this specification, the number of carbon atoms in the alkyl group mentioned above also includes the number of carbon atoms constituting the heterocycle.

[0753] For R 1d The alkyl group may have the above-mentioned substituents, preferably halogen atoms, straight-chain or branched alkyl groups with 1 to 10 carbon atoms or cyclic alkyl groups with 3 to 10 carbon atoms, hydroxyl groups, and particularly preferably methyl or ethyl groups.

[0754] As R 1d The alkyl group mentioned above preferably does not contain a carbonyl group.

[0755] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0756] The alkyl group described above preferably does not have any substituents.

[0757] As R 1d Preferably, it is a straight-chain or branched alkyl group with or without substituents, having 1 to 10 carbon atoms, or a cyclic alkyl group with or without substituents, having 3 to 10 carbon atoms. More preferably, it is a straight-chain or branched alkyl group without carbonyls, having 1 to 10 carbon atoms, or a cyclic alkyl group without carbonyls, having 3 to 10 carbon atoms. Even more preferably, it is a straight-chain or branched alkyl group without substituents, having 1 to 3 carbon atoms. Particularly preferred are methyl (-CH3) or ethyl (-C2H5), and most preferably methyl (-CH3).

[0758] In equation (d), R 2d and R 4d Independently H or substituent. Two or more Rs 2d and R 4d They can be the same or different.

[0759] For R 2d and R 4d The above-mentioned substituents are preferably halogen atoms, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, with methyl and ethyl groups being particularly preferred.

[0760] As R 2d and R 4dThe alkyl group mentioned above preferably does not contain a carbonyl group.

[0761] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0762] The alkyl group described above preferably does not have any substituents.

[0763] For R 2d and R 4d The alkyl group described above is preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group, or a cyclic alkyl group with 3 to 10 carbon atoms that does not contain a carbonyl group. More preferably, it is a straight-chain or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a straight-chain or branched alkyl group with 1 to 3 carbon atoms that does not have a substituent. Methyl (-CH3) or ethyl (-C2H5) is particularly preferred.

[0764] As R 2d and R 4d H or a straight-chain or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group is preferred, H or a straight-chain or branched alkyl group with 1 to 3 carbon atoms that does not have a substituent is more preferred, H, methyl (-CH3) or ethyl (-C2H5) is even more preferred, and H is particularly preferred.

[0765] In equation (d), R 3d It is an alkylene group with 1 to 10 carbon atoms, with or without substituents. R 3d When there are more than two, they can be the same or different.

[0766] The aforementioned alkylene groups preferably do not contain carbonyl groups.

[0767] In the aforementioned alkylene groups, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkylene groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0768] The aforementioned alkylene groups preferably do not have any substituents.

[0769] As the aforementioned alkylene groups, preferably straight-chain or branched alkylene groups with or without substituents having 1 to 10 carbon atoms, or cyclic alkylene groups with or without substituents having 3 to 10 carbon atoms, preferably straight-chain or branched alkylene groups without carbonyls having 1 to 10 carbon atoms, or cyclic alkylene groups without carbonyls having 3 to 10 carbon atoms, more preferably straight-chain or branched alkylene groups without substituents having 1 to 10 carbon atoms, and even more preferably methylene (-CH2-), ethylene (-C2H4-), isopropylene (-CH(CH3)CH2-), or propylene (-C3H6-).

[0770] R 1d R 2d R 3d and R 4d Any two of them can bond together to form a ring.

[0771] In formula (d), n is an integer of 1 or more. Preferably, n is an integer from 1 to 40, more preferably an integer from 1 to 30, and even more preferably an integer from 5 to 25.

[0772] In equation (d), p and q are independently integers greater than or equal to 0. p is preferably an integer from 0 to 10, more preferably 0 or 1. q is preferably an integer from 0 to 10, more preferably an integer from 0 to 5.

[0773] The sum of n, p, and q is preferably an integer of 6 or more. More preferably, the sum of n, p, and q is an integer of 8 or more. Furthermore, the sum of n, p, and q is 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.

[0774] In equation (d), A d -SO3X d or -COOX d (X d For H, metal atoms, NR 5d 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5d It can be H or an organic group (preferably a fluorine-free organic group, which can be the same or different). As R 5d The organic group in R is preferably alkyl. 5d Preferably, the metal atom is H or an organic group having 1 to 10 carbon atoms; more preferably, it is H or an organic group having 1 to 4 carbon atoms; and even more preferably, it is 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), with Na, K, or Li being preferred. d It can be a metal atom or NR 5d 4(R 5d (As mentioned above).

[0775] As X d H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR are preferred. 5d 4. From the perspective of easy solubility in water, H, Na, K, Li or NH4 are more preferred; from the perspective of even easier solubility in water, Na, K or NH4 are further preferred; Na or NH4 are particularly preferred; and from the perspective of easy removal, NH4 is the most preferred. d When the surfactant is NH4, it exhibits excellent solubility in aqueous media and is unlikely to leave metal residues in TFE-based polymers or final products.

[0776] In equation (d), L is a single bond, -CO2-B- -OCO-B- -CONR 6d -B- -NR 6d CO-B- Or -CO- (where -CO2-B-, -OCO-B-, -CONR) 6d -B-、-NR 6d (excluding the carbonyl group contained in CO-B-), B is a single bond or an alkylene group with or without substituents, having 1 to 10 carbon atoms, R 6d It is H or an alkyl group having 1 to 4 carbon atoms, with or without substituents. More preferably, the alkylene group has 1 to 5 carbon atoms. Furthermore, more preferably, the R group... 6d It is H or methyl. This refers to A in the formula. d The bonded side.

[0777] Ideally, L should be a single bond.

[0778] Examples of surfactants (d) mentioned above include: CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2COOK. 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ぁ (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONaぁ (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONaぁ 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.

[0779] Surfactant (d) can be manufactured by, for example, the manufacturing method described in International Publication No. 2020 / 022355.

[0780] Next, the surfactant (e) will be explained.

[0781] In equation (e), R 1e ~R 5e Represents H or a monovalent substituent, where R 1e and R 3e At least one of the general formulas in the formula is: -Y e -R 6e The group shown, R 2e and R 5e At least one of the following represents the general formula: -X e -A e The indicated group, or general formula: -Y e -R 6e The group shown. R 1e ~R 5e Any two of them can bond together to form a ring.

[0782] For R 1e The alkyl group may have the above-mentioned substituents, preferably halogen atoms, straight-chain or branched alkyl groups with 1 to 10 carbon atoms or cyclic alkyl groups with 3 to 10 carbon atoms, hydroxyl groups, and particularly preferably methyl or ethyl groups.

[0783] As R 1e The alkyl group mentioned above preferably does not contain a carbonyl group.

[0784] In the above-mentioned alkyl groups, less than 75% of the hydrogen atoms bonded to the carbon atoms can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0785] The alkyl group described above preferably does not have any substituents.

[0786] As R 1e Preferably, it is a straight-chain or branched alkyl group with or without substituents, having 1 to 10 carbon atoms, or a cyclic alkyl group with or without substituents, having 3 to 10 carbon atoms. More preferably, it is a straight-chain or branched alkyl group without carbonyls, having 1 to 10 carbon atoms, or a cyclic alkyl group without carbonyls, having 3 to 10 carbon atoms. Even more preferably, it is a straight-chain or branched alkyl group without substituents, having 1 to 3 carbon atoms. Particularly preferred are methyl (-CH3) or ethyl (-C2H5), and most preferably methyl (-CH3).

[0787] As a monovalent substituent, the preferred general formula is: -Y e -R 6e The indicated group, general formula: -X e -A e The indicated groups, -H, and C with or without substituents are shown. 1-20 Alkyl groups, -NH2, -NHR 9e (R 9e Organic groups (preferably fluorine-free organic groups), -OH, -COOR 9e (R 9e (Organic groups (preferably fluorine-free organic groups)) or -OR 9e (R 9e The alkyl group is an organic group (preferably a fluorine-free organic group). The number of carbon atoms in the alkyl group is preferably 1 to 10.

[0788] As R 9e C is preferred 1-10 alkyl or C 1-10 alkyl carbonyl, more preferably C 1-4 alkyl or C1-4 alkyl carbonyl group.

[0789] In the formula, X e The presence of the same or different elements in each instance indicates a divalent linking group or bond.

[0790] R 6e In the absence of any one of carbonyl, ester, amide, and sulfonyl groups, X is preferred. e It is a divalent linker comprising at least one group selected from the group consisting of carbonyl, ester, amide and sulfonyl groups.

[0791] As X e Preferably, it includes -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, and -CONR. 8e -and-NR 8e At least one divalent linking group of the group consisting of CO-, C 1-10 alkylene groups, or bonded bonds. R 8e It represents H or an organic group (preferably a fluorine-free organic group).

[0792] As R 8e The organic group in R is preferably alkyl. 8e H or C are preferred 1-10 Organic groups, more preferably H or C 1-4 Organic groups, preferably H or C 1-4 Alkyl groups, and more preferably H.

[0793] In equation (e), A e The same or different occurrences indicate -COOM e -SO3M e or -OSO3M e (M e For H, metal atoms, NR 7e 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7e It is an H or an organic group (preferably a fluorine-free organic group). 4 Rs 7e (They can be the same or different). In equation (e), A e -COOM e It is one of the preferred methods.

[0794] As R 7e The organic group in R is preferably alkyl. 7e H or C are preferred 1-10 Organic groups, more preferably H or C 1-4Organic groups, preferably H or C 1-4 Alkyl groups.

[0795] Examples of metal atoms that can be used as the aforementioned metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0796] As M e H, metal atoms or NR are preferred. 7e 4. More preferably, H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR. 7e 4. Further preferred materials include H, Na, K, Li or NH4, even more preferred materials include Na, K or NH4, particularly preferred materials include Na or NH4, and most preferred materials include NH4.

[0797] In equation (e), Y e The fact that they appear the same or different indicates that the choice is free from -S(=O)2-, -O-, -COO-, -OCO-, -CONR. 8e -and-NR 8e The divalent linking group or bond in the group composed of CO-, R 8e It represents H or an organic group (preferably a fluorine-free organic group).

[0798] As Y e Preferred bonding bonds, with free choice of -O-, -COO-, -OCO-, -CONR 8e -and-NR 8e The divalent linking group in the group consisting of CO-, more preferably the linking group consisting of -COO- and -OCO-, is preferred.

[0799] As R 8e The organic group in R is preferably alkyl. 8e H or C are preferred 1-10 Organic groups, more preferably H or C 1-4 Organic groups, preferably H or C 1-4 Alkyl groups, and more preferably H.

[0800] In equation (e), R 6e The presence of the same or different occurrences indicates that at least one alkyl group selected from the group consisting of carbonyl, ester, amide, and sulfonyl groups may be present between carbon atoms, having a carbon number of two or more. The above R 6e The number of carbon atoms in the organic group (preferably a fluorine-free organic group) is preferably 2 to 20, more preferably 2 to 10.

[0801] R 6eThe alkyl group may contain one or more of at least one group selected from the group consisting of carbonyl, ester, amide, and sulfonyl groups between carbon atoms, but these groups are not included at the end of the alkyl group. The above R 6e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0802] As R 6e Preferred: General formula: -R 10e -CO-R 11e The groups shown General formula: -R 10e -COO-R 11e The groups shown General formula: -R 11e The groups shown General formula: -R 10e -NR 8e CO-R 11e The indicated groups, or General formula: -R 10e -CONR 8e -R 11e The groups shown, (where R is in the formula) 8e Represents H or an organic group (preferably a fluorine-free organic group). R 10e alkylene, R 11e (Alkyl groups, with or without substituents).

[0803] As R 6e More preferably, the general formula is: -R 10e -CO-R 11e The group shown.

[0804] As R 8e The organic group in R is preferably alkyl. 8e H or C are preferred 1-10 Organic groups, more preferably H or C 1-4 Organic groups, preferably H or C 1-4 Alkyl groups, and more preferably H.

[0805] R 10e The alkylene group preferably has 1 or more carbon atoms, more preferably 3 or more, more preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. Additionally, R 10e The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 3 to 10.

[0806] R 11e The alkyl group can have 1 to 20 carbon atoms, preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 6, even more preferably 1 to 3, especially preferably 1 or 2, and most preferably 1. Furthermore, the above-mentioned R is preferred. 11e The alkyl group consists only of primary, secondary, and tertiary carbons, and is particularly preferred to consist only of primary and secondary carbons. That is, as R 11e The preferred compounds are methyl, ethyl, n-propyl, and isopropyl, with methyl being the most preferred.

[0807] In equation (e), R 2e and R 5e At least one of them is a general formula: -X e -A e The group shown, A e -COOM e It is also one of the preferred methods.

[0808] As the surfactant (e), the compound represented by general formula (e-1), the compound represented by general formula (e-2), or the compound represented by general formula (e-3) is preferred, and the compound represented by general formula (e-1) or the compound represented by general formula (e-2) is more preferred.

[0809] General formula (e-1): [Chemistry 56]

[0810] (where R is in the formula) 3e ~R 6e X e A e and Y e (as described above); General formula (e-2): [Chemistry 57]

[0811] (where R is in the formula) 4e ~R 6e X e A e and Y e (as described above); General formula (e-3): [Chem.58] (where R is in the formula) 2e R 4e ~R 6e X e A e and Ye (As mentioned above).

[0812] As a general formula: -X e -A e The indicated groups are preferably: -COOM e , -R 12e COOM e , -SO3M e , -OSO3M e , -R 12e SO3M e , -R 12e OSO3M e , -OCO-R 12e -COOM e , -OCO-R 12e -SO3M e , -OCO-R 12e -OSO3M e , -COO-R 12e -COOM e , -COO-R 12e -SO3M e , -COO-R 12e -OSO3M e , -CONR 8e -R 12e -COOM e , -CONR 8e -R 12e -SO3M e , -CONR 8e -R 12e -OSO3M e , -NR 8e CO-R 12e -COOM e , -NR 8e CO-R 12e -SO3M e , -NR 8e CO-R 12e-OSO3M e , -OS(=O)2-R 12e -COOM e , -OS(=O)2-R 12e -SO3M e ,or -OS(=O)2-R 12e -OSO3M e , (where R is in the formula) 8e and M e As described above. R 12e C 1-10 Alkylene).

[0813] The above R 12e In the alkylene group, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkylene groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0814] As a general formula: -Y e -R 6e The indicated groups are preferably: General formula: -R 10e -CO-R 11e The groups shown General formula: -OCO-R 10e -CO-R 11e The groups shown General formula: -COO-R 10e -CO-R 11e The groups shown General formula: -OCO-R 10e -COO-R 11e The groups shown General formula: -COO-R 11e The groups shown General formula: -NR 8e CO-R 10e -CO-R 11e The indicated groups, or General formula: -CONR 8e -R 10e -NR 8e CO-R 11e The groups shown, (where R is in the formula) 8e R 10e and R 11e (As mentioned above).

[0815] In the formula, R is used as 4e and R 5e H or C are preferred independently. 1-4 Alkyl groups.

[0816] The above R 4e and R 5e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0817] R in the general formula (e-1) 3e Preferably H or C with or without substituents. 1-20 Alkyl groups, more preferably H or C without substituents. 1-20 Alkyl groups, preferably H.

[0818] The above R 3e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0819] R in general formula (e-3) 2e Preferably, H, OH, or C with or without substituents are used. 1-20 Alkyl groups, more preferably H, OH, or C without substituents. 1-20 Alkyl groups, preferably H or OH.

[0820] The above R 2e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atom can be replaced by halogen atoms, less than 50% can be replaced by halogen atoms, less than 25% can be replaced by halogen atoms, and preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0821] Surfactant (e) can be manufactured using known manufacturing methods.

[0822] The aforementioned specific hydrocarbon surfactants are preferably carboxylic acid type hydrocarbon surfactants. As for the aforementioned carboxylic acid type hydrocarbon surfactants, there are no limitations as long as they have a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is replaced by an inorganic cation (e.g., a metal atom, ammonium, etc.). For example, the aforementioned specific hydrocarbon surfactants can be used that have a carboxyl group or a group in which the hydrogen atom of the carboxyl group is replaced by an inorganic cation.

[0823] The aforementioned carboxylic acid-based hydrocarbon surfactant preferably has a fluorine atom substitution ratio of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0824] As the above-mentioned carboxylic acid type hydrocarbon surfactant, it is preferred to be a surfactant having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is replaced by an inorganic cation (e.g., a metal atom, ammonium, etc.) from at least one of the surfactants (c) and (d) shown in the above formula (c) and the surfactant (d) shown in the above formula (d).

[0825] Furthermore, the aforementioned specific hydrocarbon surfactants are preferably sulfonic acid type hydrocarbon surfactants. As for the aforementioned sulfonic acid type hydrocarbon surfactants, there are no limitations as long as they have a -SO3H group, a -OSO3H group, or a group in which the hydrogen atoms of these groups are replaced by inorganic cations (e.g., metal atoms, ammonium, etc.). For example, hydrocarbon surfactants with -SO3H groups, -OSO3H groups, or groups in which the hydrogen atoms of these groups are replaced by inorganic cations can be used.

[0826] The sulfonic acid-based hydrocarbon surfactants described above preferably have a fluorine atom substitution ratio of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0827] The TFE-based polymer composition disclosed herein can be efficiently manufactured using only at least one of the aforementioned specific hydrocarbon surfactants. Furthermore, the TFE-based polymer composition disclosed herein can be manufactured using two or more of the aforementioned specific hydrocarbon surfactants simultaneously, or using other surface-active compounds besides the aforementioned specific hydrocarbon surfactants, as long as they are volatile or can remain in the molded body or the like made of the TFE-based polymer.

[0828] Other compounds with surface-active properties may be used, for example, the substances described in Japanese Patent Application Publication Nos. 2013-542308, 2013-542309, and 2013-542310.

[0829] Other compounds with surface-active properties can be surfactants with both hydrophilic and hydrophobic portions on the same molecule, such as hydrocarbon surfactants. They can be cationic, nonionic, or anionic.

[0830] The proportion of hydrogen atoms bonded to carbon atoms in the above-mentioned compounds that are replaced by fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0831] Cationic surfactants typically have positively charged hydrophilic portions, such as alkylated ammonium bromide and alkylated ammonium halide, and hydrophobic portions, such as long-chain fatty acids.

[0832] The proportion of hydrogen atoms bonded to carbon atoms in the aforementioned cationic surfactant that are replaced by fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unreplaced by fluorine atoms).

[0833] Anionic surfactants typically have hydrophilic moieties such as carboxylates, sulfonates, or sulfates, and hydrophobic moieties such as alkyl groups as long-chain hydrocarbon moieties.

[0834] The proportion of hydrogen atoms bonded to carbon atoms in the aforementioned anionic surfactant that are replaced by fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unreplaced by fluorine atoms).

[0835] Nonionic surfactants typically do not contain charged groups and have a hydrophobic portion that is a long-chain hydrocarbon. The hydrophilic portion of nonionic surfactants contains water-soluble functional groups such as ethylene ether chains derived from the polymerization of ethylene oxide.

[0836] The nonionic surfactants described above preferably have a fluorine atom substitution ratio of 50% or less for hydrogen atoms bonded to carbon atoms, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0837] Examples of nonionic surfactants

[0838] Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerides, and their derivatives.

[0839] Specific examples of polyoxyethylene alkyl ethers include: polyoxyethylene lauryl ether, polyoxyethylene hexadecyl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, and polyoxyethylene docosyl ether.

[0840] Specific examples of polyoxyethylene alkylphenyl ethers include: polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, etc.

[0841] Specific examples of polyoxyethylene alkyl esters include: polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.

[0842] Specific examples of sorbitan alkyl esters include: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0843] Specific examples of polyoxyethylene sorbitan alkyl esters include: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0844] Specific examples of glycerides include: glyceryl monotetradecanoate, glyceryl monostearate, and glyceryl monooleate.

[0845] Specific examples of the above derivatives include: polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, and polyoxyethylene alkyl ether phosphates.

[0846] The above-mentioned ethers and esters can have HLB values ​​of 10 to 18.

[0847] Examples of nonionic surfactants include Dow Chemical Company's Triton X series (X15, X45, X100, etc.), Tergitol 15-S series, Tergitol TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol L series, BASF's Pluronic R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)), and Iconol TDA series (TDA-6, TDA-9, TDA-10).

[0848] Examples of anionic hydrocarbon surfactants include Versatic 10 (registered trademark) manufactured by Resolution Performance Products and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0849] Other compounds with surface-active properties include anionic surfactants represented by RLM (where R is a straight-chain or branched alkyl group with or without substituents, or a cyclic alkyl group with or without substituents, having or without substituents, having 3 or more carbon atoms; in the case of 3 or more carbon atoms, it may contain monovalent or divalent heterocycles, or may form a ring; L is -ArSO3-, -SO3-, -SO4-, -PO3-, or -COO-, M is H, a metal atom, NR...). 5 4(R 5They can be the same or different, and can be H or an organic group (preferably a fluorine-free organic group), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. -ArSO3- is an aryl sulfonate. R 5 Preferably, it is an organic group with H or 1 to 10 carbon atoms, more preferably an organic group with H or 1 to 4 carbon atoms.

[0850] Specifically, examples include lauryl acids, which are composed of CH3-(CH2). n The substance is represented by -LM (where n is an integer from 6 to 17. L and M are the same as above).

[0851] Alternatively, a mixture of substances in which R is an alkyl group having 12 to 16 carbon atoms and LM is a sulfate or sodium dodecyl sulfate (SDS) can be used.

[0852] Other compounds with surface active energy can also be cited as examples of those derived from R. 6 (-LM)2 represents an anionic surfactant (where R is an anionic surfactant). 6 It is a straight-chain or branched alkylene group with one or more carbon atoms, with or without substituents, or a cyclic alkylene group with three or more carbon atoms, with or without substituents. When there are three or more carbon atoms, it may contain monovalent or divalent heterocycles, or it may form a ring. L is -ArSO3-, -SO3-, -SO4-, -PO3-, or -COO-, and M is H, a metal atom, or NR. 5 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5 It is H or an organic group (preferably a fluorine-free organic group), and -ArSO3- is an aryl sulfonate.

[0853] Other compounds with surface active energy can also be cited as examples of those derived from R. 7 (-LM)3 represents an anionic surfactant (where R is an anionic surfactant). 7 It is a straight-chain or branched alkyne group with one or more carbon atoms, with or without substituents, or a cyclic alkyne group with three or more carbon atoms, with or without substituents. When there are three or more carbon atoms, it may contain monovalent or divalent heterocycles, or form a ring. L is -ArSO3-, -SO3-, -SO4-, -PO3-, or -COO-, and M is H, a metal atom, or NR. 5 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5 It is an H or an organic group (preferably a fluorine-free organic group). -ArSO3- is an aryl sulfonate.

[0854] Examples of siloxane surfactants include those described in Silicon Surfactants, R.M.Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of a siloxane surfactant comprises a clearly defined hydrophobic and a hydrophilic moiety. The hydrophobic moiety contains one or more dialkylsiloxane units, where the substituents on the silicon atoms are entirely hydrocarbons.

[0855] When the carbon atom of the hydrocarbon group can be replaced by halogens such as fluorine, these siloxane surfactants can also be regarded as hydrocarbon surfactants in the sense that they are completely replaced by hydrogen atoms, that is, the monovalent substituent on the carbon atom of the hydrocarbon group is hydrogen.

[0856] The aforementioned siloxane surfactant preferably has a fluorine atom substitution ratio of 50% or less for hydrogen atoms bonded to carbon atoms, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted by fluorine atoms).

[0857] Regarding siloxane-based surfactants, it is also disclosed in U.S. Patent No. 6,841,616.

[0858] Examples of anionic hydrocarbon surfactants based on siloxanes include Noveon (a registered trademark) manufactured by Lubrizol Advanced Materials, Inc., and SilSense, available from Consumer Specialties. TM PE-100 silicone, SilSense TM CA-1 silicone, etc.

[0859] As anionic hydrocarbon surfactants, examples include Lankropol (registered trademark) K8300, a sulfosuccinate surfactant manufactured by Akzo Nobel Surface Chemistry LLC.

[0860] Examples of sulfosuccinate surfactants include diisodecyl sulfosuccinate Na salt (Emulsogen SB10 manufactured by Clariant) and diisotridecyl sulfosuccinate Na salt (Polirol TR / LNA manufactured by Cesapinia Chemicals).

[0861] Other compounds with surface-active properties include PolyFox surfactant (registered trademark) manufactured by Omnova Solutions, Inc.TM PF-156A, PolyFox TM (PF-136A, etc.).

[0862] As other compounds with surface-active properties, anionic hydrocarbon surfactants are preferred. The substances described above can be used as anionic hydrocarbon surfactants, and the following hydrocarbon surfactants are also preferred.

[0863] Examples of anionic hydrocarbon surfactants include, for instance, the compound (α) represented by formula (α):

[0864] (where R is in the formula) 100 It is a monovalent organic group containing one or more carbon atoms (preferably a fluorine-free organic group). M is H, a metal atom, or NR. 101 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 101 It can be H or an organic group (preferably a fluorine-free organic group, which can be the same or different). As R 101 The organic group is preferably alkyl. As R 101 Preferably, H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms is preferred, and even more preferably H or an alkyl group having 1 to 4 carbon atoms is preferred.

[0865] From the perspective of surface activity energy, R 100 The number of carbon atoms is preferably 2 or more, more preferably 3 or more. Furthermore, from the perspective of water solubility, R... 100 The number of carbon atoms is preferably 29 or less, more preferably 23 or less.

[0866] Examples of metal atoms that can serve as M include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred. For M, H, a metal atom, or NR are preferred. 101 4. More preferably, H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR. 101 4. Further preferred materials include H, Na, K, Li or NH4, even more preferred materials include Na, K or NH4, particularly preferred materials include Na or NH4, and most preferred materials include NH4.

[0867] As for the aforementioned compound (α), examples can also be given by R. 102 -COOM represents an anionic surfactant (where R is an anionic surfactant). 102It is a straight-chain or branched alkyl, alkenyl, alkylene, or alkenyl group with one or more carbon atoms, having or without substituents, or a cyclic alkyl, alkenyl, alkylene, or alkenyl group with or without substituents, having or without substituents, and may contain ether bonds. In the case of three or more carbon atoms, it may contain monovalent or divalent heterocycles, or may form a ring. (M is the same as above).

[0868] Specifically, examples include CH3-(CH2) n -COOM (where n is an integer from 2 to 28. M is the same as above) represents the substance.

[0869] From the perspective of emulsification stability, the above compound (α) may not contain carbonyl groups (except for the carbonyl groups in the carboxyl group).

[0870] As the aforementioned hydrocarbon-containing surfactants that do not contain carbonyl groups, compounds of the following formula (A1) are preferably examples:

[0871] (where R is in the formula) 103 It is an alkyl, alkenyl, alkylene, or alkenyl group containing 6 to 17 carbon atoms, and may contain ether bonds. M is H, a metal atom, or NR. 101 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphatonium with or without substituents. R 101 Whether the groups are the same or different, they are H or organic groups (preferably fluorine-free organic groups)).

[0872] In the above formula (A1), R 103 Preferably alkyl or alkenyl (they may contain ether groups). The above R 103 The alkyl or alkenyl groups can be linear or branched. The above R... 103 The number of carbon atoms is not limited, for example, it can be 2 to 29.

[0873] When the above alkyl groups are in the form of straight chains, R 103 The number of carbon atoms is preferably 3 to 29, more preferably 5 to 23. When the alkyl group is branched, R... 103 The number of carbon atoms is preferably 5 to 35, more preferably 11 to 23.

[0874] When the above alkenyl groups are linear, R 103 The number of carbon atoms is preferably 2 to 29, more preferably 9 to 23. When the alkenyl group is branched, R... 103 The number of carbon atoms is preferably 2 to 29, more preferably 9 to 23.

[0875] Examples of the alkyl and alkenyl groups mentioned above include methyl, ethyl, isobutyl, tert-butyl, vinyl, etc.

[0876] Examples of the aforementioned compounds (α) include butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, heptadecanic acid, stearic acid, oleic acid, isoleic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)-linolenic acid, tungsten acid, arachidic acid, 8,11-eicosadienoic acid, medelic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, ceric acid, linalic acid, beeswax acid, crotonic acid, and myristate oil. Acids, palmitoleic acid, cis-6-hexadecenoic acid, transoleic acid, codoleic acid, eicosapentaenoic acid, erucic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, terpineic acid, α-tungsten acid, β-tungsten acid, di-hypothalamic-gamma-linolenic acid, eicosatrienoic acid, octadecanoic acid, arachidonic acid, eicosatraenoic acid, adrenal acid, borsenoic acid, eicosapentaenoic acid, docosapentaenoic acid, stigmata, tetradecanoic acid, docosahexaenoic acid, herring acid, and their salts.

[0877] In particular, it is preferred to select at least one from the group consisting of lauric acid, decanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, and their salts.

[0878] Examples of the above-mentioned salts include the hydrogen atom of the carboxyl group in the metal atom of formula M and NR. 11 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, without particular limitation.

[0879] In addition, as an anionic hydrocarbon surfactant, compounds (β) represented by the following formula (β) can also be cited as examples:

[0880] (where R is in the formula) 100 It is a monovalent organic group containing one or more carbon atoms (preferably a fluorine-free organic group). M is H, a metal atom, or NR. 101 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 101 It can be H or an organic group (preferably a fluorine-free organic group, which can be the same or different). As R 101 The organic group is preferably alkyl. As R 101 Preferably, H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms is preferred, and even more preferably H or an alkyl group having 1 to 4 carbon atoms is preferred.

[0881] From the perspective of surface activity energy, R100 The number of carbon atoms is preferably 2 or more, more preferably 3 or more. Furthermore, from the perspective of water solubility, R... 100 The number of carbon atoms is preferably 29 or less, more preferably 23 or less.

[0882] Examples of metal atoms that can serve as M include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred. For M, H, a metal atom, or NR are preferred. 101 4. More preferably, H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR. 101 4. Further preferred materials include H, Na, K, Li or NH4, even more preferred materials include Na, K or NH4, particularly preferred materials include Na or NH4, and most preferred materials include NH4.

[0883] As for the aforementioned compound (β), examples can also be derived from R. 102 -SO3M represents an anionic surfactant (where R is an anionic surfactant). 102 It is a straight-chain or branched alkyl, alkenyl, alkylene, or alkenyl group with one or more carbon atoms, having or without substituents, or a cyclic alkyl, alkenyl, alkylene, or alkenyl group with or without substituents, having or without substituents, and may contain ether bonds. In the case of three or more carbon atoms, it may contain monovalent or divalent heterocycles, or may form a ring. (M is the same as above).

[0884] Specifically, examples include CH3-(CH2) n The substance is represented by -SO3M (where n is an integer from 2 to 28. M is the same as above).

[0885] From the perspective of emulsion stability, the above compound (β) may not contain carbonyl groups (except for the carbonyl groups in the carboxyl group).

[0886] As the aforementioned hydrocarbon-containing surfactant that does not contain carbonyl groups, compounds of formula (B1) are preferably exemplified, for example:

[0887] (where R is in the formula) 103 It is an alkyl, alkenyl, alkylene, or alkenyl group containing 6 to 17 carbon atoms, and may contain ether bonds. M is H, a metal atom, or NR. 101 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphatonium with or without substituents. R 101 Whether the groups are the same or different, they are H or organic groups (preferably fluorine-free organic groups)).

[0888] In equation (B) above, R 103 Preferably alkyl or alkenyl (they may contain ether groups). The above R103 The alkyl or alkenyl groups can be linear or branched. The above R... 103 The number of carbon atoms is not limited, for example, it can be 2 to 29.

[0889] When the above alkyl groups are in the form of straight chains, R 103 The number of carbon atoms is preferably 3 to 29, more preferably 5 to 23. When the alkyl group is branched, R... 103 The number of carbon atoms is preferably 5 to 35, more preferably 11 to 23.

[0890] When the above alkenyl groups are linear, R 103 The number of carbon atoms is preferably 2 to 29, more preferably 9 to 23. When the alkenyl group is branched, R... 103 The number of carbon atoms is preferably 2 to 29, more preferably 9 to 23.

[0891] Examples of the alkyl and alkenyl groups mentioned above include methyl, ethyl, isobutyl, tert-butyl, vinyl, etc.

[0892] Examples of the aforementioned compound (β) include sulfonic acids, aliphatic, unsaturated aliphatic, and aromatic sulfonic acids, as well as their salts.

[0893] Examples of the aforementioned sulfonic acids include 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, perfluorobutanesulfonic acid, linear alkylbenzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, DBS, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, and butylnaphthalenesulfonic acid. Examples of the aforementioned sulfates include sodium alkyl sulfate, α-sulfonyl fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, α-olefin sulfonate, lauryl sulfate, myristyl sulfate, lauryl alcohol polyether sulfate, and polyoxyethylene alkylphenol sulfonic acid.

[0894] As the aforementioned compound (β), at least one of the following groups is particularly preferred: saturated aliphatic and aromatic sulfates and their salts; more preferably, at least one of the following groups is preferred: sodium alkyl sulfate, α-sulfonyl fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, α-olefin sulfonate, lauryl sulfate, myristyl sulfate, lauryl ether sulfate, polyoxyethylene alkylphenol sulfonic acid, and their salts.

[0895] Examples of salts described above include those where the hydrogen atom of the sulfonic acid group is a metal atom of formula M, and NR. 11 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, without particular limitation.

[0896] Examples of anionic hydrocarbon surfactants include surfactants (1-0A) represented by the formula (1-0A): [Chemistry 59]

[0897] (where R is in the formula) 1A ~R 5A The carbon group can be H, a monovalent hydrocarbon group that may contain ester groups between carbon atoms, or the general formula: -X A -A represents the group. Wherein, R... 2A and R 5A At least one of the following represents the general formula: -X A -A represents the group.

[0898] X A The same or different in each occurrence, consisting of a divalent hydrocarbon group or a bond; A may be the same or different in each occurrence, and is -COOM (M is H, a metal atom, or NR). 7 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7 It is an H group or an organic group (preferably a fluorine-free organic group); R 1A ~R 5A Any two of them can bond together to form a ring.

[0899] In general formula (1-0A), R 1A ~R 5A In this process, the number of carbon atoms in the monovalent hydrocarbon group that may contain an ester group between carbon atoms is preferably 1 to 50, more preferably 5 to 20. 1A ~R 5A Any two of them can bond together to form a ring. As a monovalent hydrocarbon group that can contain an ester group between carbon atoms, an alkyl group is preferred.

[0900] In the formula, X A In this embodiment, the number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 50, more preferably 5 to 20. Examples of divalent hydrocarbon groups include alkylene groups and alkanediols, with alkylene groups being preferred.

[0901] In general formula (1-0A), R 2A and R 5A Any one of them is preferably the above general formula: -X A The group represented by -A, R 2A More preferably, it is the above general formula: -X A -A represents the group.

[0902] In general formula (1-0A), R is the most suitable method. 2A General formula: -X A -A represents the group, R 1A R 3A R 4A and R 5A In the case of H, X... A Preferably, it is a bonded alkylene group or an alkylene group having 1 to 5 carbon atoms.

[0903] In addition, in general formula (1-0A), R is a suitable method. 2A General formula: -X A -A represents the group, R 1A and R 3A For -Y A -R 6 The shown groups, Y A The same or different occurrences are -COO-, -OCO-, or combined bonds, R 6 In the case where each occurrence is the same or different and is an alkyl group having two or more carbon atoms, R is preferred. 4A and R 5A For H.

[0904] Examples of hydrocarbon surfactants represented by general formula (1-0A) include glutaric acid or its salts, adipic acid or its salts, pimelic acid or its salts, octanoic acid or its salts, azelaic acid or its salts, sebacic acid or its salts.

[0905] In addition, the aliphatic carboxylic acid hydrocarbon surfactants shown in general formula (1-0A) can be 2-chain 2-hydrophilic synthetic surfactants. For example, as Gemini surfactants, examples include Geminisurf (Chukyo Oils & Fats Co., Ltd.), Gemsurf α142 (12 carbon atoms lauryl), Gemsurf α102 (10 carbon atoms), and Gemsurf α182 (14 carbon atoms).

[0906] Compound I, represented by the following formula I, can also be cited as an anionic hydrocarbon surfactant:

[0907] (In the formula, R is a hydrophobic hydrocarbon moiety containing one or more saturated or unsaturated, acyclic or cyclic aliphatic groups. The total percentage of CH3 groups in the one or more aliphatic groups relative to the total percentage of CH3, CH2 and CH groups is at least about 70%, and the hydrophobic moiety does not contain siloxane units. Each X can be the same or different, representing the ionic hydrophilic moiety. Each Z can be the same or different, representing one or more counterions of the ionic hydrophilic moiety. n is 1 to 3).

[0908] Compound I exhibits low reactivity with polymerization initiators and / or the free radicals of the fluorinated polymers grown in the emulsion polymerization of fluorinated monomers.

[0909] Compound I preferably contains the substitution moiety shown in the following formula: [Transformation 60] (where Y) + (It can be hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal or alkaline earth metal).

[0910] Compound I is preferably compound II as shown in formula II below: [Chemistry 61]

[0911] (where R is in the formula) 2’ and R 2’’’ Whether the groups are the same or different, they are saturated or unsaturated, acyclic or cyclic aliphatic groups having 4 to 16 carbon atoms, R 2’ and R 2’’’ The total percentage of CH3 groups relative to the total percentage of CH3, CH2, and CH groups is at least about 70%, or R 2’ and R 2’’’ Together, they can form a saturated or unsaturated aliphatic ring, which may contain ether or ester bonds. The total percentage of CH3 groups in the ring relative to the total percentage of CH3, CH2, and CH groups is at least about 70%. 1 It can be hydrogen, methoxy, ethoxy, or phenoxy. + (It can be hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal or alkaline earth metal).

[0912] As compound II, the following compounds are preferred, for example.

[0913] [Chemistry 62]

[0914] Y in the above formula + It can be hydrogen, ammonium, or alkali metal.

[0915] Compound I is also preferably compound III as shown in formula III below: [Chemistry 63]

[0916] (where R is in the formula) 3 R 4’ and R 4’’ Whether the groups are the same or different, they are hydrogen or saturated or unsaturated, acyclic or cyclic aliphatic groups having 4 to 16 carbon atoms, R 3R 4’ and R 4’’ The total percentage of CH3 in the groups relative to the total percentage of CH3, CH2, and CH groups is at least about 70%. Among them, R... 3 R 4’ and R 4’’ At least one of them is not hydrogen, R 4’ and R 4’’ In the case of hydrogen, R 3 Not hydrogen, R 3 In the case of hydrogen, R 4’ and R 4’’ Not hydrogen. Y + (It can be hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal or alkaline earth metal).

[0917] As compound III, the following compounds are preferred, for example.

[0918] [Chemistry 64]

[0919] Y in the above formula + It can be hydrogen, ammonium, or alkali metal.

[0920] The TFE-based polymer composition disclosed herein can be obtained even without using the aforementioned specific hydrocarbon surfactant by a manufacturing method including the following polymerization step: in the presence of a hydrocarbon surfactant and a polymerization initiator, in an aqueous medium with a pH of 4.0 or higher, only tetrafluoroethylene is polymerized, or tetrafluoroethylene and a modified monomer capable of copolymerizing with the aforementioned tetrafluoroethylene are polymerized, to obtain the TFE-based polymer.

[0921] Conventionally, polymerization initiators exhibiting acidity are used in the polymerization process for manufacturing TFE-based polymers, resulting in an aqueous medium with a pH less than 4.0. Through in-depth research, the inventors unexpectedly discovered that by using an aqueous medium with a pH of 4.0 or higher for polymerization, the stability of the polymerization is improved, enabling the production of high molecular weight TFE-based polymers.

[0922] In the above manufacturing method, tetrafluoroethylene is polymerized only in an aqueous medium with a pH of 4.0 or higher, or tetrafluoroethylene is polymerized with a modified monomer capable of copolymerizing with the aforementioned tetrafluoroethylene. A pH of 4.0 or higher is acceptable, preferably greater than 4.0, more preferably 4.5 or higher, further preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, especially preferably 6.5 or higher, especially preferably 7.0 or higher, especially preferably 7.5 or higher, and especially preferably 8.0 or higher. The upper limit of the pH is not particularly limited; for example, it can be 13.0 or lower. From the perspective of corrosion of the polymerization reactor, a pH of 12.0 or lower is preferred, more preferably 11.5 or lower, and even more preferably 11.0 or lower.

[0923] The pH value mentioned above can be measured using a pH meter.

[0924] In the above manufacturing method, the method of making the pH of the aqueous medium 4.0 or higher is not limited. For example, using an alkaline aqueous solution, using an aqueous dispersion that shows alkalinity, or using a pH adjuster to make the pH 4.0 or higher is not particularly limited.

[0925] Furthermore, even when using polymerization initiators that exhibit acidity when dissolved in aqueous media, the pH can be adjusted to 4.0 or higher by adding alkaline compounds such as sodium hydroxide. These alkaline compounds simply dissolve in water and ionize to produce OH-. - Any compound can be used, such as hydroxides of alkali metals like sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc., without particular limitation. The above polymerization process may include the step of adding an alkali compound to an aqueous medium.

[0926] The above manufacturing method allows the pH of the aqueous medium to be 4.0 or higher throughout the entire polymerization process. Alternatively, the pH can be 4.0 or higher during the middle or later stages of the polymerization process. Furthermore, the pH can be 4.0 or higher during both the middle and later stages of the polymerization process.

[0927] In the above-mentioned polymerization process, the pH of the aqueous medium is preferably 4.0 or higher for at least 60% (preferably 70% or higher, more preferably 8% or higher, further preferably 10% or higher, even more preferably 15% or higher, particularly more preferably 18% or higher, even more preferably 20% or higher, especially preferably 25% or higher) of the period from the start of polymerization until the polymer solids concentration reaches 3% by mass (preferably 70% or higher, more preferably 80% or higher, further preferably 90% or higher, even more preferably 95% or higher, especially more preferably 99% or higher, especially preferably 100%).

[0928] The pH of the aqueous medium is preferably 4.0 or higher during the period from the moment when the polymer solids concentration is 10% by mass (preferably 8% by mass, more preferably 5% by mass, further preferably 3% by mass, and even more preferably the start of polymerization) to the moment when the polymer solids concentration is 15% by mass.

[0929] In the above polymerization process, the pH of the aqueous medium is preferably 4.0 or higher for at least 60% (preferably 70% or higher, more preferably 80% or higher, further preferably 90% or higher, even more preferably 95% or higher, particularly preferably 99% or higher, especially preferably 100%) from the moment when the polymer solids concentration is 15% by mass to the moment when the polymer solids concentration is 18% by mass (preferably 20% by mass, more preferably 25% by mass).

[0930] The pH of the aqueous medium is preferably 4.0 or higher during the period from the moment when the polymer solids concentration is 25% by mass (preferably 20% by mass, more preferably 18% by mass, further preferably 15% by mass, even more preferably 10% by mass, particularly more preferably 8% by mass, especially preferably 5% by mass, more preferably 3% by mass, and even more preferably the start of polymerization) to the moment when polymerization ends.

[0931] The pH of the above-mentioned aqueous medium is preferably greater than 4.0, more preferably 4.5 or above, even more preferably 5.0 or above, even more preferably 5.5 or above, particularly more preferably 6.0 or above, especially preferably 6.5 or above, more preferably 7.0 or above, even more preferably 7.5 or above, and even more preferably 8.0 or above.

[0932] In the above manufacturing method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid hydrocarbon surfactant. There are no particular limitations on the anionic or carboxylic acid hydrocarbon surfactant; for example, compounds (α) exemplified among the other compounds with surface activity described above may be used appropriately.

[0933] In the above manufacturing method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and also preferably a sulfonic acid type hydrocarbon surfactant. There are no particular limitations on whether the hydrocarbon surfactant is anionic or sulfonic acid type. For example, compounds such as (β) exemplified among the other compounds with surface-active properties described above can be used appropriately.

[0934] The TFE-based polymer composition disclosed herein can be obtained even without using the aforementioned specific hydrocarbon surfactant by a polymerization step comprising polymerizing tetrafluoroethylene alone in an aqueous medium in the presence of an anionic hydrocarbon surfactant and a polymerization initiator, or polymerizing tetrafluoroethylene with a modified monomer capable of copolymerizing the aforementioned tetrafluoroethylene to obtain the TFE-based polymer, wherein the aforementioned hydrocarbon surfactant comprises a salt of the hydrocarbon surfactant. In other words, at least a portion of the anionic hydrocarbon surfactant in the aforementioned polymerization step is in the form of a salt.

[0935] The inventors conducted in-depth research and unexpectedly discovered that by including anionic hydrocarbon surfactants in the salts of anionic hydrocarbon surfactants, the stability of polymerization is improved, and TFE-based polymers with large molecular weights can be manufactured.

[0936] The aforementioned anionic hydrocarbon surfactants will be described later.

[0937] The presence of salts of the aforementioned anionic hydrocarbon surfactants can be confirmed by measuring their conductivity.

[0938] In the above manufacturing method, the concentration of the salt of the anionic hydrocarbon surfactant relative to the total mass of the anionic hydrocarbon surfactant is preferably 50% by mass, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, particularly more preferably 90% by mass or more, and especially preferably 95% by mass or more.

[0939] The proportion of the above-mentioned salts can be determined by the solution concentration and conductivity.

[0940] In the above manufacturing method, the hydrocarbon surfactant is more preferably a carboxylic acid type hydrocarbon surfactant. The above hydrocarbon surfactant is fluorine-free.

[0941] In the salts of anionic hydrocarbon surfactants, the cations that replace the hydrogen atoms of the acid (excluding the hydrogen atoms) are, for example, metal atoms, NR... y 4(R yThe groups can be the same or different, and can be H or an organic group (preferably a fluorine-free organic group), imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. The above R... y H or alkyl is preferred, H or alkyl with 1 to 10 carbon atoms is more preferred, and H or alkyl with 1 to 4 carbon atoms is even more preferred.

[0942] The aforementioned cations in the salts of anionic hydrocarbon surfactants are preferably metal atoms or NR atoms. y 4. More preferably NR y 4. Further optimize NH4.

[0943] Conductivity varies greatly with temperature. Therefore, a constant temperature bath is used to maintain the sample liquid temperature at 25°C, and the temperature of the pH meter cell is also kept constant before measuring conductivity.

[0944] In the above manufacturing method, the polymerization step is preferably carried out in the absence of the aforementioned hydrocarbon surfactant in the form of an organic acid. By carrying out the polymerization in the absence of the aforementioned hydrocarbon surfactant in the form of an organic acid, the stability of the polymerization is further improved, and high molecular weight TFE-based polymers can be obtained.

[0945] Essentially, the absence of the aforementioned hydrocarbon surfactant in the form of an organic acid means that the concentration of the organic acid relative to the mass of the obtained aqueous dispersion is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, especially more preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less.

[0946] In this specification, "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 -SO3H group. From the perspective of ease of adjusting the pH of an aqueous solution containing an organic acid, carboxylic acids are preferred.

[0947] In addition, "the form of organic acid" refers to the form in which the hydrogen atoms of the acidic groups (such as -COOH group, -SO3H group, etc.) contained in the organic acid are not free.

[0948] In the above manufacturing method, the hydrocarbon surfactant is an anionic hydrocarbon surfactant.

[0949] In the above polymerization process, the amount of hydrocarbon surfactant at the start of polymerization is preferably greater 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, further preferably 80 ppm or more, and even more preferably 100 ppm or more. There is no particular upper limit, but for example, 10,000 ppm is preferred, and 5,000 ppm is more preferred. By using the amount of hydrocarbon surfactant at the start of polymerization within the above range, the average primary particle size is smaller, resulting in an aqueous dispersion with superior stability.

[0950] It should be noted that polymerization can be said to begin when gaseous TFE in the reactor transforms into a TFE-based polymer and when the pressure in the reactor decreases. US Patent No. 3,391,099 (Punderson) discloses the dispersion polymerization of tetrafluoroethylene in an aqueous medium, which consists of two independent stages: first, the formation of polymer nuclei as nucleation sites, and then a growth stage involving the polymerization of the established particles. It should be noted that polymerization typically begins when both the monomer to be polymerized and the polymerization initiator are filled into the reactor. Furthermore, in this disclosure, the additive involved in the formation of nucleation sites is a nucleating agent.

[0951] The polymerization process described above preferably includes an addition step in which the composition containing a hydrocarbon surfactant is added after the polymerization has begun. This addition step further improves the stability of the polymerization and yields TFE-based polymers with higher molecular weights.

[0952] The aforementioned hydrocarbon surfactants can be in the form of solids (e.g., hydrocarbon surfactant powders) or liquids.

[0953] The above composition may contain only a hydrocarbon surfactant, or it may be a solution or dispersion of a hydrocarbon surfactant containing both a hydrocarbon surfactant and a liquid medium. Therefore, the above-described addition step can also be described as adding the hydrocarbon surfactant monomer or the composition containing the hydrocarbon surfactant after the polymerization has begun.

[0954] Hydrocarbon surfactants are not limited to one type; they can also be a mixture of two or more types.

[0955] The liquid medium can be either an aqueous medium or an organic solvent, or a combination of aqueous medium and organic solvent.

[0956] Specifically, examples of the above-mentioned compositions include aqueous solutions of hydrocarbon surfactants dissolved in an aqueous medium and aqueous dispersions of hydrocarbon surfactants dispersed in an aqueous medium.

[0957] The hydrocarbon surfactant added in the above-mentioned addition process is preferably 0.0001 to 10% by mass relative to the aqueous medium. More preferably, it is 0.001% by mass or more, further preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more, relative to the aqueous medium. Furthermore, more preferably, it is 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less, relative to the aqueous medium.

[0958] From the perspective of improving the stability of polymerization and obtaining TFE-based polymers with higher molecular weight, the above composition is preferably an aqueous solution containing a hydrocarbon surfactant and having a pH of 5.0 or higher.

[0959] The pH of the above-mentioned aqueous solution is more preferably 6.0 or higher, further preferably 6.5 or higher, even more preferably 7.0 or higher, particularly preferably 7.5 or higher, and especially preferably 8.0 or higher. Furthermore, the upper limit of the pH is not particularly limited and can be 12.0 or lower, or even 11.0 or lower.

[0960] The hydrocarbon surfactant used in the above-mentioned addition process is preferably anionic hydrocarbon surfactant, and more preferably carboxylic acid hydrocarbon surfactant.

[0961] There are no particular limitations on anionic hydrocarbon surfactants and carboxylic acid hydrocarbon surfactants; for example, compounds (α) exemplified among the other compounds with surface activity described above may be used appropriately.

[0962] The carboxylic acid-type hydrocarbon surfactant used in the above polymerization and addition steps is preferably selected from the above surfactant (e) and the above formula: R 6 (-LM)2 represents an anionic surfactant, and the above formula: R 7 At least one of the following groups is included in the anionic surfactant group shown in (-LM)3: a substance having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is replaced by an inorganic cation (e.g., a metal atom, ammonium, etc.); the above-mentioned compound (α); the above-mentioned surfactant (1-0A); and surfactants after free radical treatment or oxidation treatment of these surfactants. The above-mentioned carboxylic acid type hydrocarbon surfactant may be used as one type or as a mixture of two or more types.

[0963] The above compound (α) includes not only the above formula: R 102 -COOM(where R is the formula) 102The anionic hydrocarbon surfactant (preferably the compound shown in formula (A1)) shown in formula RLM (where R, L and M are the same as above), and also include anionic surfactants shown in formula RLM (where R, L and M are the same as above), substances having a carboxyl group (-COOH) or a group in surfactants (c) and surfactants (d) where the hydrogen atom of the carboxyl group is replaced by an inorganic cation (e.g., a metal atom, ammonium, etc.).

[0964] The aforementioned carboxylic acid-type hydrocarbon surfactant is preferably the aforementioned compound (α), more preferably a compound selected from the above formula (A1) or A in the above formula (c). c For -COOX c The compound, A in formula (d) above d For -COOX d The compound, A in the above formula (e) e -COOM e The compound is selected from the group consisting of a compound of formula (1-0A) where A is -COOM, and surfactants formed by free radical treatment or oxidation of the compound, and more preferably from the group consisting of a compound of formula (A1) and surfactants formed by free radical treatment or oxidation of the compound.

[0965] In particular, at least one of the following groups is preferred: lauric acid, decanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid and their salts, and compounds formed by free radical treatment or oxidation of these compounds. Examples of such salts include those with a hydrogen atom of the carboxyl group in the form of a metal atom of formula M, NR, etc. 101 4. Substances with or without substituents, such as imidazolynes, pyridinium, or phosphonium, are not particularly limited.

[0966] The above manufacturing method preferably involves polymerizing tetrafluoroethylene in the absence of a fluorinated surfactant.

[0967] In the above manufacturing method, "substantially in the absence of fluorinated surfactant" means that, relative to the aqueous medium, the fluorinated surfactant is 10 ppm by mass or less, preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably less than 10 ppb by mass, even more preferably less than 10 ppb by mass, even more preferably less than 1 ppb by mass, and particularly preferably less than 1 ppb by mass.

[0968] In addition, "in the absence of fluorinated surfactants" also means that no fluorinated surfactants were intentionally added.

[0969] Examples of fluorinated surfactants include anionic fluorinated surfactants.

[0970] The aforementioned anionic fluorinated surfactants can be, for example, surfactants containing fluorine atoms in which the total number of carbon atoms in the portion excluding the anionic groups is 20 or less.

[0971] Alternatively, the fluorinated surfactant described above may be a fluorinated surfactant with an anionic moiety having a molecular weight of 1000 or less, preferably 800 or less.

[0972] It should be noted that the "anionic portion" mentioned above refers to the portion of the fluorinated surfactant other than the cationic portion. For example, in F(CF2) shown in formula (I) described later. n1 In the case of COOM, it is "F(CF2)". n1 The "COO" part.

[0973] Specifically, examples of the aforementioned fluorinated surfactants include U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 142541, U.S. Patent Application Publication No. 2008 / 0015319, and U.S. Patent No. 3250808. Fluorinated surfactants described in patents such as U.S. Patent No. 3,271,341, Japanese Patent Application Publication No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, International Publication No. 2007 / 119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, and International Publication No. 2013 / 189826.

[0974] Examples of anionic fluorinated surfactants include those with the general formula (N... 0 The compound shown is ).

[0975] As mentioned above, examples of anionic fluorinated surfactants include carboxylic acid-based fluorinated surfactants and sulfonic acid-based fluorinated surfactants.

[0976] The TFE-based polymer composition disclosed herein can be suitably manufactured by a manufacturing method comprising an addition step of adding at least one of a decomposing agent selected from the group consisting of a free radical scavenger and a polymerization initiator. The addition step is performed in a step of emulsion polymerization in an aqueous medium. By adding a free radical scavenger or a decomposing agent of the polymerization initiator, the free radical concentration during polymerization can be adjusted. From the perspective of reducing the free radical concentration, a free radical scavenger is preferred.

[0977] As the aforementioned free radical scavengers, compounds that do not possess the ability to re-initiate after addition or chain transfer into the polymerization system are used. Specifically, compounds with the following functions are used: readily undergoing chain transfer reactions with primary or growth free radicals to generate stable free radicals that do not react with monomers; or readily undergoing addition reactions with primary or growth free radicals to generate stable free radicals.

[0978] The activity of substances commonly referred to as chain transfer agents is characterized by chain transfer constants and re-initiation efficiency. Among chain transfer agents, substances with a re-initiation efficiency of essentially 0% are called free radical scavengers.

[0979] The aforementioned free radical scavengers can also be described as compounds whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant, and whose re-initiation efficiency is substantially zero%. "Substantially zero re-initiation efficiency" means that the generated free radicals make the free radical scavenger a stable free radical.

[0980] Preferably, the compound is a compound with a chain transfer constant (Cs) with TFE at the polymerization temperature (= chain transfer rate constant (kc) / polymerization rate constant (kp)) greater than 0.1. More preferably, the chain transfer constant (Cs) of the above compound is 0.5 or more, further preferably 1.0 or more, even more preferably 5.0 or more, and particularly preferably 10 or more.

[0981] As the free radical scavenger described above in this disclosure, it is preferably selected from at least one of the following groups: aromatic hydroxyl compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and copper chloride (CuCl2).

[0982] Examples of aromatic hydroxyl compounds include non-substituted phenols, polyphenols, salicylic acid, meta-salicylic acid or para-salicylic acid, gallic acid, naphthol, etc.

[0983] Examples of non-substituted phenols include o-nitrophenol, m-nitrophenol, or p-nitrophenol, o-aminophenol, m-aminophenol, or p-aminophenol, and p-nitrosophenol. Examples of polyphenols include catechol, resorcinol, hydroquinone, pyrogallol, pyrogallol, naphthol, and resorcinol.

[0984] Examples of aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and benzidine.

[0985] Examples of the aforementioned quinone compounds include ortho-benzoquinone, meta-benzoquinone or para-benzoquinone, 1,4-naphthoquinone, alizarin, etc.

[0986] Examples of thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN).

[0987] As the aforementioned free radical scavenger, aromatic hydroxyl compounds are preferred, non-substituted phenols or polyphenols are more preferred, and hydroquinone is even more preferred.

[0988] From the perspective of reducing the standard proportion, the amount of the aforementioned free radical scavenger added is preferably equivalent to 3 to 500% (molar basis) of the polymerization initiator concentration. More preferably, the lower limit is 5% (molar basis), further preferably 8% (molar basis), more preferably 10% (molar basis), even more preferably 15% (molar basis), particularly preferably 20% (molar basis), especially preferably 25% (molar basis), particularly preferably 30% (molar basis), and particularly preferably 35% (molar basis). More preferably, the upper limit is 400% (molar basis), further preferably 300% (molar basis), even more preferably 200% (molar basis), and especially preferably 100% (molar basis).

[0989] As a decomposing agent for the polymerization initiator, any compound capable of decomposing the polymerization initiator used is acceptable, and preferably at least one is selected from the group consisting of sulfites, bisulfites, bromates, diimides, 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), and examples of iron salts include ferric(II) sulfate.

[0990] The amount of the decomposing agent of the above-mentioned polymerization initiator added is in the range of 25% to 300% by mass relative to the amount of oxidant in the polymerization initiator (redox initiator group described later). Preferably, it is 25% to 150% by mass, more preferably 50% to 100% by mass.

[0991] From the perspective of reducing the standard proportion, the amount of decomposing agent added to the above-mentioned polymerization initiator is preferably equivalent to 3 to 500% (molar basis) of the polymerization initiator concentration. More preferably, the lower limit is 5% (molar basis), further preferably 8% (molar basis), further preferably 10% (molar basis), further preferably 13% (molar basis), and even more preferably 15% (molar basis). More preferably, the upper limit is 400% (molar basis), further preferably 300% (molar basis), even more preferably 200% (molar basis), and particularly preferably 100% (molar basis).

[0992] The TFE-based polymer, preferably formed in an aqueous medium, is added at a concentration of 5% by mass or more, preferably from the group consisting of a free radical scavenger and a polymerization initiator decomposer. More preferably, it is added at a concentration of 10% by mass or more.

[0993] Furthermore, it is preferable to add the TFE-based polymer formed in the aqueous medium when the concentration is 40% by mass or less. More preferably, it is added when the concentration is 35% by mass or less, and even more preferably, it is added when the concentration is 30% by mass or less.

[0994] The above-mentioned addition process can be a process of continuously adding at least one of the decomposing agents selected from the group consisting of free radical scavengers and polymerization initiators.

[0995] At least one of the decomposing agents selected from the group consisting of free radical scavengers and polymerization initiators is added continuously, for example, not all at once, but over time and without interruption or in batches.

[0996] The above polymerization process can further polymerize tetrafluoroethylene in the presence of a nucleating agent.

[0997] As the nucleating agent mentioned above, it is preferably selected from at least one of the group consisting of fluorinated polyethers, nonionic surfactants and chain transfer agents.

[0998] In this case, the above-mentioned polymerization process is preferably a process in which tetrafluoroethylene is polymerized in an aqueous medium in the presence of a hydrocarbon surfactant and the above-mentioned nucleating agent to obtain a TFE-based polymer.

[0999] As the aforementioned fluorinated polyether, perfluoropolyether is preferred.

[1000] The fluorinated polyethers described above preferably have repeating units as shown in formulas (1a) to (1d).

[1001]

[1002] (In equations (1a) to (1d), m and n are integers greater than or equal to 1).

[1003] As the aforementioned fluorinated polyether, a fluorinated polyether acid or a salt thereof is preferred. The fluorinated polyether acid is preferably a carboxylic acid, sulfonic acid, sulfonamide, or phosphonic acid, and more preferably a carboxylic acid. Among the fluorinated polyether acid or its salt, a salt of a fluorinated polyether acid is preferred, an ammonium salt of a fluorinated polyether acid is more preferred, and an ammonium salt of a fluorinated polyether carboxylic acid is even more preferred.

[1004] The aforementioned fluoropolyether acids or their salts can have any chain structure in which the oxygen atom in the molecular backbone is separated by a saturated fluorocarbon group having 1 to 3 carbon atoms. Two or more types of fluorocarbon groups can exist in the molecule.

[1005] As the above-mentioned fluoropolyether acid or its salt, the preferred compounds are those shown in the following formula or their salts: 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, (In the formula, m and n are the same as above).

[1006] These structures were studied by Kasai in J. Appl. Polymer Sci., 57, 797 (1995). As disclosed herein, such fluorinated polyethers may have carboxylic acid groups or their salts at one or both ends. Similarly, such fluorinated polyethers may have sulfonic acid or phosphonic acid groups or their salts at one or both ends. Furthermore, fluorinated polyethers with acid functional groups at both ends may have different groups at each end. Regarding monofunctional fluorinated polyethers, the other end of the molecule is usually perfluorinated, but may also contain hydrogen or chlorine atoms.

[1007] Fluorinated polyethers having acid groups at one or both ends have at least two ether oxygen atoms, preferably at least four ether oxygen atoms, and more preferably at least six ether oxygen atoms. Preferably, at least one of the fluorocarbon groups separating the ether oxygen atoms has two or three carbon atoms, more preferably at least two such fluorocarbon groups have two or three carbon atoms. More preferably, at least 50% of the fluorocarbon groups separating the ether oxygen atoms have two or three carbon atoms. Additionally, it is preferred that the fluorinated polyethers have at least 15 carbon atoms in total, for example, the minimum value of n or n+m in the repeating unit structure described above is at least 5. Two or more fluorinated polyethers having acid groups at one or both ends can be used in the method based on this disclosure. Typically, fluorinated polyethers can contain two or more compounds in various proportions within a molecular weight range relative to the average molecular weight, unless special care is taken when manufacturing a single type of specific fluorinated polyether compound.

[1008] The aforementioned fluorinated polyethers preferably have a number-average molecular weight of 800 g / mol or higher. Fluorinated polyether acids or their salts may be difficult to disperse in aqueous media; therefore, their number-average molecular weight is preferably less than 6000 g / mol. More preferably, the number-average molecular weight of the fluorinated polyether acid or its salt is 800–3500 g / mol, and even more preferably 1000–2500 g / mol.

[1009] The amount of the above-mentioned fluorinated polyether relative to the aqueous medium is preferably 5 to 3000 ppm, more preferably 5 to 2000 ppm, further preferably 10 ppm, and further preferably 100 ppm.

[1010] For nonionic surfactants used as nucleating agents, examples of such nonionic surfactants can be cited, with fluorine-free nonionic surfactants being preferred. For instance, compounds represented by the following general formula (i) can be cited as examples of such nonionic surfactants:

[1011] (where R is in the formula) 3 A is a straight-chain or branched primary or secondary alkyl group with 8 to 18 carbon atoms. 1 (It consists of polyoxyethylene chains).

[1012] R 3 The number of carbon atoms is preferably 10 to 16, more preferably 12 to 16. 3 When the number of carbon atoms is 18 or less, it is difficult to obtain good dispersion stability in aqueous dispersions. Additionally, R... 3 When the number of carbon atoms is greater than 18, the flow temperature is high, making it difficult to process. R 3 When the number of carbon atoms is less than 8, the surface tension of the aqueous dispersion increases, and its permeability and wettability are easily reduced.

[1013] Polyoxyethylene chains can be composed of ethylene oxide and propylene oxide. A polyoxyethylene chain consisting of an average repeating number of 5–20 for vinyl oxide groups and an average repeating number of 0–2 for propylene oxide groups, and containing hydrophilic groups, is described. The number of ethylene oxide units can include either a commonly provided broad or narrow unimodal distribution, or a broader or bimodal distribution obtained...

Claims

1. A tetrafluoroethylene-based polymer composition used as an adhesive for electrochemical devices, wherein, The average particle size of the tetrafluoroethylene-based polymer composition is 1 μm to 300 μm, and the average aspect ratio is 2.0 or less.

2. The tetrafluoroethylene-based polymer composition according to claim 1, wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymeric units and hexafluoropropylene-based polymeric units.

3. The tetrafluoroethylene-based polymer composition as described in claim 1 or 2, wherein it is in the form of a powder.

4. The tetrafluoroethylene-based polymer composition according to any one of claims 1 to 3, used as a binder for lithium-ion secondary batteries, wherein the composition is in the form of a powder.

5. An adhesive for electrochemical devices, substantially composed solely of a tetrafluoroethylene-based polymer composition, wherein, The average particle size of the tetrafluoroethylene-based polymer composition is 1 μm to 300 μm, and the average aspect ratio is 2.0 or less.

6. The adhesive for electrochemical devices as described in claim 5, wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymeric units and hexafluoropropylene-based polymeric units.

7. The adhesive for electrochemical devices as described in claim 5 or 6, wherein, The apparent density of the tetrafluoroethylene-based polymer composition is less than 0.40 g / ml.

8. The adhesive for electrochemical devices according to any one of claims 5 to 7, wherein, The tetrafluoroethylene-based polymer composition is non-melt processable.

9. The adhesive for electrochemical devices according to any one of claims 5 to 8, wherein, The tetrafluoroethylene-based polymer composition comprises a fluorinated compound having a hydrophilic group.

10. The adhesive for electrochemical devices as described in claim 9, wherein, The fluorinated compound having hydrophilic groups has a molecular weight of less than 1000.

11. The adhesive for electrochemical devices as described in claim 9 or 10, wherein, The hydrophilic group is selected from -SO3M. a -SO2M a -OSO2M a -PO3M a -COOM a -OCOM a and -OM a At least one of the groups, In the formula, M a -H, metal atom, -NR 1 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 1 It is an H or an organic group.

12. The adhesive for electrochemical devices according to any one of claims 9 to 11, wherein, The fluorinated compound having a hydrophilic group has the following general formula (N 0 The compound shown is a compound. In the formula, X n0 For H, Cl, or F, Rf n0 It is a chain, branched, or cyclic alkylene group with 3 to 20 carbon atoms, in which some or all of the H atoms are replaced by F atoms. The alkylene group may contain one or more ether bonds, and some of the H atoms may be replaced by Cl atoms. 0 It is an anionic group.

13. The adhesive for electrochemical devices as described in claim 9, wherein, The fluorinated compound with hydrophilic groups is a polymeric compound with ionic groups.

14. The adhesive for electrochemical devices as described in claim 13, wherein, The ionic group is selected from -SO3M. a -SO2M a -PO3M a and -COOM a At least one of the groups, In the formula, M a -H, metal atom, -NR 1 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 1 It is an H or an organic group.

15. The adhesive for electrochemical devices as described in claim 13 or 14, wherein, The content of the ionic groups is 0.8 meq / g or more relative to the polymer compound.

16. The adhesive for electrochemical devices according to any one of claims 13 to 15, wherein, The ion exchange rate of the polymer compound is below 53.

17. The adhesive for electrochemical devices according to any one of claims 13 to 16, wherein, The polymeric compound is selected from at least one polymer (I) comprising a polymeric 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): In the formula, X 1 and X 3 Each is independently F, Cl, H or CF3; A 0 It is an anionic group; X 2 It is H, F, alkyl or fluorinated alkyl; R is a linking group; Z 1 and Z 2 Each is independently H, F, alkyl, or fluorinated alkyl; m is an integer greater than or equal to 1. General Formula (II): In the formula, R FA1 is -Rf 1 p -R F -O q - R FA2 is -Rf 2 p -R FX -O q - , R F It is a divalent fluorinated polyether group. R FX It is a divalent fluorinated polyether group containing anionic groups. Rf 1 and Rf 2 Each can be independently represented by a C atom that is substituted with one or more fluorine atoms. 1-6 Alkylene p can be 0 or 1 independently. Each q is independently either 0 or 1. X A Each group is independently a single bond or a 2- to 10-valent group. T X and T X Each can be independently selected from (i) C1 to C2 groups containing one or more of H, O, and Cl, and without the aforementioned anionic groups. 24 (ii) Hydrogen (fluorine) hydrocarbon group and (ii) C1-C1 groups containing at least one of the aforementioned anionic groups. 24 A group composed of (hydrogen) and (fluorine) hydrocarbon groups.

18. The adhesive for electrochemical devices as described in claim 10 or 11, wherein, The fluorinated compound having a hydrophilic group is at least one selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), a perfluoroether carboxylic acid (III) represented by general formula (III), and a polymer comprising a polymeric unit (1A) based on a monomer represented by general formula (1A). In the formula, m ranges from 4 to 20, and M 1 For H, metal atoms, NR 5 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphorium with or without substituents, p = 1 or 2, R 5 Whether the groups are the same or different, they are H or organic groups with 1 to 10 carbon atoms. In the formula, n is 4 to 20, M 2 For H, metal atoms, NR 5 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, where q is 1 or 2, R 5 Same as above, In the formula, Rf 1 It is a perfluoroalkyl group with 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is as defined above. In the formula, Rf is a fluorinated alkylene group with 1 to 40 carbon atoms, or a fluorinated alkylene group with ether bonds having 2 to 100 carbon atoms, and A is -COOM. a -SO3M a -OSO3M a -SO2M a Or C(CF3)2OM a M a -H, metal atom, -NR 2 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 2 It is an H or an organic group.

19. The binder for electrochemical devices according to any one of claims 5 to 18, wherein it is a powder.

20. The binder for electrochemical devices according to any one of claims 5 to 19, wherein it is a binder for lithium-ion secondary batteries.

21. A tetrafluoroethylene-based polymer composition used as an adhesive for electrochemical devices, wherein, The average particle size of the tetrafluoroethylene-based polymer composition is 1 μm to 300 μm, and the proportion of particles with an aspect ratio of 3.0 or higher is less than 15%.

22. The tetrafluoroethylene-based polymer composition of claim 21, wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymeric units and hexafluoropropylene-based polymeric units.

23. The tetrafluoroethylene-based polymer composition as described in claim 21 or 22, wherein it is in the form of a powder.

24. The tetrafluoroethylene-based polymer composition according to any one of claims 21 to 23, used as a binder for lithium-ion secondary batteries, wherein the composition is in the form of a powder.

25. An adhesive for electrochemical devices, substantially composed solely of a tetrafluoroethylene-based polymer composition, wherein, The average particle size of the tetrafluoroethylene-based polymer composition is 1 μm to 300 μm, and the proportion of particles with an aspect ratio of 3.0 or higher is less than 15%.

26. The adhesive for electrochemical devices as described in claim 25, wherein, The tetrafluoroethylene-based polymer composition comprises a tetrafluoroethylene-based polymer. The tetrafluoroethylene-based polymer is selected from at least one of the following groups: homopolymers of tetrafluoroethylene and modified polytetrafluoroethylene comprising tetrafluoroethylene-based polymeric units and hexafluoropropylene-based polymeric units.

27. The binder for electrochemical devices as described in claim 25 or 26, wherein it is in the form of a powder.

28. The binder for electrochemical devices as described in any one of claims 25 to 27, wherein it is a binder for lithium-ion secondary batteries.

29. An electrode binder comprising a tetrafluoroethylene polymer composition according to any one of claims 1-4, 21-24, or an electrochemical device binder and an electrode active substance according to any one of claims 5-20, 25-28.

30. The electrode mixture as described in claim 29, wherein it is in the form of a sheet.

31. An electrode comprising a tetrafluoroethylene-based polymer composition according to any one of claims 1 to 4, 21 to 24, or an electrochemical device binder, an electrode active material, and a current collector according to any one of claims 5 to 20, 25 to 28.

32. A secondary battery comprising the electrode as described in claim 31.

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