Tetrafluoroethylene polymer composition, binder for solid secondary battery, mixture for electrolyte layer, electrode mixture, electrode, and solid secondary battery

Abstract

Provided are: a TFE-based polymer composition for a binder for a solid secondary battery, said TFE-based polymer composition being capable of improving the strength of a mixture sheet; and the like. A TFE-based polymer composition which is used in a binder for a solid secondary battery and which contains a TFE-based polymer and at least one compound selected from the group consisting of compounds represented by general formulae (1) and (2). General formula (1): (H-(CF2) m-1-COO) pM1 (in the formula, m is 4-20, M1 is H, a metal atom, NR54 (R5 may be the same or different and is H or an organic group having 1-10 carbon atoms) or the like, and p is 1 or 2. ) General formula (2): (H-(CF2) n-SO3) qM2 (in the formula, n is 4-20, M2 is H, a metal atom, NR54 (R5 is the same as above) or the like, and q is 1 or 2. ).

Description

Technical Field

[0001] The present invention relates to a tetrafluoroethylene polymer composition, a binder for a solid secondary battery, a mixture for an electrolyte layer, an electrode mixture, an electrode and a solid secondary battery. Background Art

[0002] Secondary batteries such as lithium-ion secondary batteries are used in small and portable electrical and electronic devices such as notebook computers, mobile phones, smartphones, tablet computers, and ultra-notebooks due to their high voltage, high energy density, low self-discharge, low memory effect, and ability to be ultra-lightweight. They are also being put into practical use as power sources for driving vehicles and large stationary power supplies, such as in automobiles. There is a growing demand for secondary batteries to achieve higher energy density and further improve battery characteristics.

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

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

[0005] Prior art literature

[0006] Patent Literature

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

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

[0009] Patent Document 3: International Publication No. 2021 / 181888

[0010] Patent Document 4: International Publication No. 2021 / 192541

[0011] Patent Document 5: International Publication No. 2022 / 138942

[0012] Patent Document 6: International Publication No. 2022 / 138939 Summary of the Invention

[0013] Technical problem to be solved by the invention

[0014] The present invention aims to provide a tetrafluoroethylene polymer composition for a solid secondary battery binder capable of improving the strength of a mixture sheet, and a solid secondary battery binder, an electrolyte layer mixture, an electrode mixture, an electrode, and a solid secondary battery using the same.

[0015] Means of solving technical problems

[0016] The present invention (1) is a tetrafluoroethylene polymer composition used as a binder for solid-state secondary batteries, wherein the composition comprises a tetrafluoroethylene polymer and at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

[0017] General formula (1): (H-(CF2) m-1 -COO) p M 1

[0018] (where m is 4 to 20. 1 H, metal atoms, NR 5 4(R 5 (may be the same or different and be H or an organic group having 1 to 10 carbon atoms), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.)

[0019] General formula (2): (H-(CF2) n -SO3) q M 2

[0020] (where n is 4 to 20. 2 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. q is 1 or 2.

[0021] The present invention (2) is a binder for electrochemical devices, which is a binder for solid-state secondary batteries that is essentially composed only of a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition contains a tetrafluoroethylene-based polymer and at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

[0022] General formula (1): (H-(CF2) m-1 -COO) p M 1

[0023] (where m is 4 to 20. 1 H, metal atoms, NR 5 4(R 5 (may be the same or different and be H or an organic group having 1 to 10 carbon atoms), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.)

[0024] General formula (2): (H-(CF2) n -SO3) q M 2

[0025] (where n is 4 to 20. 2 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. q is 1 or 2.

[0026] The present invention (3) is the binder for solid-state secondary batteries according to the present invention (2), wherein in the above general formula (1), M 1 is H or NH4, in the above general formula (2), M 2 is H or NH4.

[0027] The present invention (4) is the binder for solid secondary batteries according to the present invention (2) or (3), wherein the tetrafluoroethylene polymer is polytetrafluoroethylene.

[0028] The present invention (5) is the binder for solid secondary batteries according to any one of the present inventions (2) to (4), wherein the content of the tetrafluoroethylene polymer is 99.95% by mass or more relative to the tetrafluoroethylene polymer composition.

[0029] The present invention (6) is a binder for solid-state secondary batteries according to any one of the present inventions (2) to (5), wherein the content of compound (1) is greater than 1 mass ppb and less than 1000 mass ppb, and the content of compound (2) is less than 5000 mass ppb, relative to the tetrafluoroethylene polymer composition.

[0030] The present invention (7) is the binder for solid secondary batteries according to any one of the present inventions (2) to (6), wherein the tetrafluoroethylene polymer composition does not substantially contain the compound represented by the following general formula (3).

[0031] General formula (3): (H-(CF2)8-SO3) q M 2

[0032] (Where M 2 H, metal atoms, NR 5 4(R 5 (may be the same or different and be H or an organic group having 1 to 10 carbon atoms), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. q is 1 or 2.)

[0033] The present invention (8) is the binder for solid secondary batteries according to the present invention (7), wherein the content of the compound represented by the general formula (3) is 25 ppb by mass or less relative to the tetrafluoroethylene polymer composition.

[0034] The present invention (9) is a binder for solid-state secondary batteries according to any one of the present inventions (2) to (8), wherein the tetrafluoroethylene polymer composition comprises at least one compound selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (4'), and their contents are all less than 1000 ppb by mass relative to the tetrafluoroethylene polymer composition.

[0035] General formula (4): (H-(CF2) 15 -COO) p M 1

[0036] (Where M 1 H, metal atoms, NR 5 4(R 5 (may be the same or different and be H or an organic group having 1 to 10 carbon atoms), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.)

[0037] General formula (4'): (H-(CF2) 16 -COO) p M 1

[0038] (Where M 1 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0039] The present invention (10) is a binder for solid-state secondary batteries according to any one of the present inventions (2) to (9), wherein the tetrafluoroethylene polymer composition comprises at least one compound selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'), and their contents are all less than 1000 ppb by mass relative to the tetrafluoroethylene polymer composition.

[0040] General formula (5): (H-(CF2) 13 -COO) p M 1

[0041] (Where M1 H, metal atoms, NR 5 4(R 5 (may be the same or different and be H or an organic group having 1 to 10 carbon atoms), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.)

[0042] General formula (5'): (H-(CF2) 14 -COO) p M 1

[0043] (Where M 1 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0044] The present invention (11) is a tetrafluoroethylene polymer composition used as a binder for solid secondary batteries, which is stretchable and has a 0.1% mass loss temperature of 400°C or lower.

[0045] The present invention (12) is a tetrafluoroethylene polymer composition used as a binder for solid-state secondary batteries, which is stretchable and has a 1.0% mass loss temperature of 492°C or lower.

[0046] The present invention (13) is a tetrafluoroethylene polymer composition used as a binder for solid-state secondary batteries, which is stretchable and has a thermal instability index (TII) of 20 or more.

[0047] The present invention (14) is a tetrafluoroethylene polymer composition used as a binder for solid-state secondary batteries, wherein the composition has a standard specific gravity of 2.200 or less and a 0.1% mass loss temperature of 400°C or less.

[0048] The present invention (15) is a tetrafluoroethylene polymer composition used as a binder for solid-state secondary batteries, wherein the standard specific gravity is 2.200 or less and the 1.0% mass loss temperature is 492°C or less.

[0049] The present invention (16) is the tetrafluoroethylene polymer composition described in the present invention (15), wherein the standard specific gravity is 2.130 or higher and the 1.0% mass loss temperature is 470°C or higher.

[0050] The present invention (17) is the tetrafluoroethylene polymer composition according to the present invention (15) or (16), wherein the tetrafluoroethylene polymer is polytetrafluoroethylene.

[0051] The present invention (18) is the tetrafluoroethylene polymer composition according to any one of the present inventions (15) to (17), wherein the content of the tetrafluoroethylene polymer is 99.95% by mass or more relative to the tetrafluoroethylene polymer composition.

[0052] The present invention (19) is a mixture for an electrolyte layer, which comprises the tetrafluoroethylene polymer composition described in any one of the present inventions (1), (11) to (18) or the binder for a solid secondary battery described in any one of the present inventions (2) to (10) and a solid electrolyte.

[0053] The present invention (20) is the electrolyte layer mixture according to the present invention (19), wherein the solid electrolyte is a sulfide-based solid electrolyte or an oxide-based solid electrolyte.

[0054] The present invention (21) is a solid-state secondary battery comprising the electrolyte layer mixture according to the present invention (20).

[0055] The present invention (22) is an electrode mixture comprising the tetrafluoroethylene polymer composition described in any one of the present inventions (1), (11) to (18) or the binder for solid-state secondary batteries described in any one of the present inventions (2) to (10), and an electrode active material.

[0056] The present invention (23) is an electrode comprising the polytetrafluoroethylene composition described in any one of the present inventions (1) and (11) to (18) or the binder for solid-state secondary batteries described in any one of the present inventions (2) to (10), an electrode active material, and a current collector.

[0057] The present invention (24) is a solid-state secondary battery comprising the electrode according to the present invention (23).

[0058] Effects of the Invention

[0059] The present invention provides a tetrafluoroethylene polymer composition for a solid secondary battery binder capable of improving the strength of a mixture sheet, and a solid secondary battery binder, an electrolyte layer mixture, an electrode mixture, an electrode, and a solid secondary battery using the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is a schematic diagram of a cross section of a pressure cell used for measuring the ion conductivity of a solid electrolyte sheet in Examples. DETAILED DESCRIPTION

[0061] In the present invention, an "organic group" refers to a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. The organic group is preferably an alkyl group which may have one or more substituents.

[0062] In the present specification, the organic group contained in the hydrocarbon-based surfactant is preferably a fluorine-free organic group.

[0063] The present invention will be described in detail below.

[0064] The present invention provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (1) of the present invention), which is a tetrafluoroethylene (TFE)-based polymer composition used as a binder for solid-state secondary batteries, wherein the composition contains a TFE-based polymer and at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

[0065] General formula (1): (H-(CF2) m-1 -COO) p M 1

[0066] (where m is 4 to 20. 1 H, metal atoms, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0067] General formula (2): (H-(CF2) n -SO3) q M 2

[0068] (where n is 4 to 20. 2 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. q is 1 or 2.

[0069] The present invention also provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (2) of the present invention), which is a TFE-based polymer composition used as a binder for solid-state secondary batteries, wherein the composition is stretchable and has a 0.1% mass loss temperature of 400°C or less.

[0070] The present invention also provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (3) of the present invention), which is a TFE-based polymer composition used as a binder for solid-state secondary batteries, wherein the composition is stretchable and has a 1.0% mass loss temperature of 492°C or less.

[0071] The present invention also provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (4) of the present invention), which is a TFE-based polymer composition used as a binder for solid-state secondary batteries, wherein the composition is stretchable and has a thermal instability index (TII) of 20 or greater.

[0072] The present invention also provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (5) of the present invention), which is a TFE-based polymer composition used as a binder for solid-state secondary batteries, wherein its standard specific gravity is less than 2.200 and its 0.1% mass loss temperature is less than 400°C.

[0073] The present invention also provides a TFE-based polymer composition (hereinafter also referred to as the TFE-based polymer composition (6) of the present invention), which is a TFE-based polymer composition used as a binder for solid-state secondary batteries, wherein its standard specific gravity is less than 2.200 and its 1.0% mass loss temperature is less than 492°C.

[0074] In this specification, unless otherwise specified, the TFE-based polymer compositions (1) to (6) of the present invention are collectively referred to as "the TFE-based polymer composition of the present invention."

[0075] The TFE-based polymer composition of the present invention has the above-mentioned structure, so it is possible to improve the strength of the composite sheet. In addition, since there is no need to use water, when used as a solid-state secondary battery binder, it is possible to suppress the deterioration of battery characteristics (such as a reduction in capacity). In addition, there is no need to use a large amount of dispersion medium such as water or an organic solvent, and the electrode active material and solid electrolyte combined can be widely selected, which is advantageous in the production process. In addition, the process and cost of using a dispersion medium can be reduced. And then, the TFE-based polymer composition of the present invention is excellent in the bonding strength with active material and electrolyte, so it is possible to reduce the amount used.

[0076] The TFE polymer composition (1) of the present invention contains at least one compound selected from the group consisting of a compound represented by the following general formula (1) (hereinafter also referred to as compound (1)) and a compound represented by the following general formula (2) (hereinafter also referred to as compound (2)). The TFE polymer compositions (2) to (6) of the present invention may contain the above-mentioned compound.

[0077] General formula (1): (H-(CF2) m-1 -COO)p M 1

[0078] (where m is 4 to 20. 1 H, metal atoms, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0079] General formula (2): (H-(CF2) n -SO3) q M 2

[0080] (where n is 4 to 20. 2 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. q is 1 or 2.

[0081] For the above M 1 and M 2 Examples of the metal atom include monovalent and divalent metal atoms, and examples include alkali metals (Group 1) and alkaline earth metals (Group 2). Specifically, examples include Na, K, and Li.

[0082] 4 Rs 5 They can be the same or different. 5 , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0083] The above M 1 and M 2 Preferred is H, an alkali metal or NH 4 , more preferably H or NH 4 .

[0084] In the general formula (1), m is preferably 6 or greater, more preferably 8 or greater, further preferably 11 or greater, still more preferably 13 or greater, and particularly preferably 15 or greater, and is preferably 18 or less, and more preferably 16 or less.

[0085] In the general formula (2), n is preferably 6 or more, more preferably 8 or more, further preferably 11 or more, still more preferably 13 or more, particularly preferably 15 or more, and is preferably 18 or less, more preferably 16 or less.

[0086] The TFE polymer composition containing compound (1) and / or (2) is obtained by using a hydrocarbon surfactant. That is, the TFE polymer composition (1) of the present invention may contain a TFE polymer and compound (1) and / or (2) and a hydrocarbon surfactant. The content of the hydrocarbon surfactant in the TFE polymer composition (1) of the present invention is not particularly limited, but is generally 100 ppm by mass to 10% by mass.

[0087] In the above hydrocarbon surfactant, the ratio of hydrogen atoms bonded to carbon atoms to be substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0088] When the TFE-based polymer composition of the present invention contains compound (1) (content greater than 0), the content of compound (1) relative to the TFE-based polymer composition may be 10 ppm by mass or less, preferably 5000 ppb by mass or less, more preferably 1000 ppb by mass or less, even more preferably 500 ppb by mass or less, still more preferably 100 ppb by mass or less, still more preferably 25 ppb by mass or less, still more preferably 15 ppb by mass or less, and particularly preferably 10 ppb by mass or less. The lower limit is not particularly limited and may be less than the quantitative lower limit, may be 0.1 ppb by mass, or may be 1 ppb by mass.

[0089] When the TFE-based polymer composition of the present invention contains compound (2) (content greater than 0), the content of compound (2) relative to the TFE-based polymer composition may be 10 ppm by mass or less, preferably 5000 ppb by mass or less, more preferably 1000 ppb by mass or less, even more preferably 500 ppb by mass or less, still more preferably 100 ppb by mass or less, still more preferably 25 ppb by mass or less, still more preferably 15 ppb by mass or less, and particularly preferably 10 ppb by mass or less. The lower limit is not particularly limited and may be less than the quantitative lower limit, may be 0.1 ppb by mass, or may be 1 ppb by mass.

[0090] The TFE-based polymer composition of the present invention preferably contains substantially no compound represented by the following general formula (3) (hereinafter also referred to as compound (3)).

[0091] General formula (3): (H-(CF2)8-SO3) q M 2

[0092] (Where M 2 H, metal atoms, NR 5 4(R 5(a) may be the same or different and is H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. q is 1 or 2.

[0093] "Substantially containing no compound (3)" means that the content of compound (3) is 25 ppb by mass or less relative to the TFE-based polymer composition. The content of compound (3) is preferably 20 ppb by mass or less, more preferably 15 ppb by mass or less, and even more preferably 10 ppb by mass or less relative to the TFE-based polymer composition. The lower limit is not particularly limited and may be 0 ppb by mass, 0.1 ppb by mass, or 1 ppb by mass.

[0094] The TFE-based polymer composition of the present invention contains at least one compound selected from the group consisting of a compound represented by the following general formula (4) (hereinafter also referred to as compound (4)) and a compound represented by the following general formula (4') (hereinafter also referred to as compound (4')), and the content of each of these compounds is preferably 1000 mass ppb or less relative to the above-mentioned TFE-based polymer composition.

[0095] General formula (4): (H-(CF2) 15 -COO) p M 1

[0096] (Where M 1 H, metal atoms, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0097] General formula (4'): (H-(CF2) 16 -COO) p M 1

[0098] (Where M 1 H, metal atoms, NR 5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0099] When the TFE-based polymer composition of the present invention contains compound (4) (content greater than 0), the content of compound (4) is more preferably 500 mass ppb or less, further preferably 250 mass ppb or less, even more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, even more preferably 25 mass ppb or less, even more preferably 15 mass ppb or less, and particularly preferably 10 mass ppb or less, relative to the TFE-based polymer composition. The lower limit is not particularly limited and may be less than the quantitative lower limit, and may be 0.1 mass ppb or 1 mass ppb.

[0100] When the TFE-based polymer composition of the present invention contains compound (4') (content greater than 0), the content of compound (4') is more preferably 500 mass ppb or less, further preferably 250 mass ppb or less, even more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, even more preferably 25 mass ppb or less, even more preferably 15 mass ppb or less, and particularly preferably 10 mass ppb or less, relative to the TFE-based polymer composition. The lower limit is not particularly limited and may be less than the quantitative lower limit, and may be 0.1 mass ppb or 1 mass ppb.

[0101] The TFE-based polymer composition of the present invention contains at least one compound selected from the group consisting of a compound represented by the following general formula (5) (hereinafter also referred to as compound (5)) and a compound represented by the following general formula (5') (hereinafter also referred to as compound (5')), and the content of each of these compounds is preferably 1000 mass ppb or less relative to the above-mentioned TFE-based polymer composition.

[0102] General formula (5): (H-(CF2) 13 -COO) p M 1

[0103] (Where M 1 H, metal atoms, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0104] General formula (5'): (H-(CF2) 14 -COO) p M 1

[0105] (Where M 1 H, metal atoms, NR5 4(R 5 Same as above), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. p is 1 or 2.

[0106] When the TFE-based polymer composition of the present invention contains compound (5) (content greater than 0), the content of compound (5) is more preferably 500 mass ppb or less, further preferably 250 mass ppb or less, even more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, even more preferably 25 mass ppb or less, even more preferably 15 mass ppb or less, and particularly preferably 10 mass ppb or less, relative to the TFE-based polymer composition. The lower limit is not particularly limited and may be less than the quantitative lower limit, and may be 0.1 mass ppb or 1 mass ppb.

[0107] When the TFE-based polymer composition of the present invention contains compound (5') (content greater than 0), the content of compound (5') is more preferably 500 mass ppb or less, further preferably 250 mass ppb or less, even more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, even more preferably 25 mass ppb or less, even more preferably 15 mass ppb or less, and particularly preferably 10 mass ppb or less, relative to the TFE-based polymer composition. The lower limit is not particularly limited and may be less than the quantitative lower limit, and may be 0.1 mass ppb or 1 mass ppb.

[0108] The contents of compounds (1), (2), (3), (4), (4'), (5), and (5') are values ​​measured using liquid chromatography-mass spectrometry as described in the Examples below.

[0109] The TFE-based polymer in the TFE-based polymer composition of the present invention can be tetrafluoroethylene (TFE) homopolymer, or can be a TFE copolymer comprising polymerized units based on TFE (TFE units) and polymerized units based on a modifying monomer (hereinafter also referred to as "modified monomer units"). The copolymer comprising above-mentioned TFE units and modified monomer units can be a modified polytetrafluoroethylene (PTFE) having a modified monomer unit of less than 10 mass %. Above-mentioned modified PTFE can comprise the TFE units more than 99.0 mass % and the modified monomer units less than 1.0 mass %. In addition, above-mentioned modified PTFE can only be composed of TFE units and modified monomer units.

[0110] The TFE-based polymer is preferably a copolymer containing TFE units and modified monomer units, and more preferably the modified PTFE, from the viewpoint of further suppressing degradation of battery characteristics and improving adhesive strength, strength, and flexibility of the composite sheet.

[0111] The TFE homopolymer means a homopolymer in which the content of polymerized units based on a modifying monomer copolymerizable with TFE in all polymerized units is less than 0.0001% by mass.

[0112] From the perspective of further suppressing the degradation of battery characteristics and improving stretchability, adhesive strength, and the strength and flexibility of the composite sheet, the TFE copolymer preferably has a content of the modified monomer units in the range of 0.00001 to 10% by mass relative to the total polymerized units. The lower limit of the content of the modified monomer units is more preferably 0.0001% by mass, further preferably 0.001% by mass, still more preferably 0.005% by mass, and even more preferably 0.010% by mass. The upper limit of the content of the modified monomer unit is preferably 5.0 mass%, more preferably 3.0 mass%, further preferably 1.0 mass%, still more preferably 0.90 mass%, still more preferably 0.80 mass%, still more preferably 0.50 mass%, still more preferably 0.40 mass%, still more preferably 0.30 mass%, still more preferably 0.20 mass%, still more preferably 0.15 mass%, still more preferably 0.10 mass%, still more preferably 0.08 mass%, particularly preferably 0.05 mass%, and most preferably 0.03 mass%.

[0113] In this specification, the modified monomer unit refers to a part of the molecular structure of the TFE-based polymer, and is a portion derived from the modified monomer.

[0114] The content of each polymerized unit can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

[0115] The modifying monomer is not particularly limited as long as it can copolymerize with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene [HFP]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as chlorotrifluoroethylene [CTFE]; perfluorovinyl ether; perfluoroallyl ether; (perfluoroalkyl)ethylene, ethylene, etc. The modifying monomer used may be one or two or more.

[0116] The perfluorovinyl ether is not particularly limited, and examples thereof include the following general formula (A):

[0117] CF2=CF-ORf(A)

[0118] (wherein Rf represents a perfluoroorganic group) and the like. In this specification, the "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0119] Examples of the perfluorovinyl ether include perfluoro(alkyl vinyl ether) [PAVE], wherein Rf in the general formula (A) is a perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

[0120] Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0121] Examples of the perfluorovinyl ether include those wherein Rf in the general formula (A) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:

[0122] [Chemistry 1]

[0123]

[0124] (wherein m represents 0 or an integer of 1 to 4), and Rf is the following formula:

[0125] [Chemistry 2]

[0126]

[0127] (wherein n represents an integer of 1 to 4) and the like.

[0128] The (perfluoroalkyl)ethylene (PFAE) is not particularly limited, and examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.

[0129] Examples of perfluoroallyl ethers include those represented by the general formula (B):

[0130] CF2=CF-CF2-ORf 1 (B)

[0131] (Where Rf 1 represents a perfluorinated organic group).

[0132] The above Rf 1Preferred are perfluoroalkyl groups having 1 to 10 carbon atoms or perfluoroalkoxyalkyl groups having 1 to 10 carbon atoms. The perfluoroallyl ether is preferably at least one selected from the group consisting of CF2=CF-CF2-O-CF3, CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9, more preferably at least one selected from the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9, and even more preferably CF2=CF-CF2-O-CF2CF2CF3.

[0133] As the above-mentioned modifying monomer, from the perspective of improving stretchability, adhesive strength and flexibility of the composite sheet, it is preferably at least one selected from the group consisting of PAVE, HFP, VDF and CTFE, more preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether) [PMVE], HFP, VDF and CTFE, and further preferably at least one selected from the group consisting of PMVE and HFP.

[0134] The TFE polymer may have a core-shell structure. Examples of the TFE polymer having a core-shell structure include particles comprising a core of a high molecular weight TFE polymer and a shell of a lower molecular weight TFE polymer or TFE copolymer.

[0135] In addition, as the TFE based polymer with core-shell structure, for example, can enumerate the core of the PTFE that comprises high molecular weight and the PTFE of low molecular weight or the modified PTFE shell of modification in particle.As such modified PTFE, for example, can enumerate the PTFE of putting down in writing in the Japanese Patent Table 2005-527652 communique.

[0136] From the perspective of forming a composite sheet with even greater strength, the TFE polymer preferably has an endothermic peak temperature of 320°C or higher, more preferably 325°C or higher, even more preferably 330°C or higher, still more preferably 335°C or higher, still more preferably 340°C or higher, still more preferably 342°C or higher, and particularly preferably 344°C or higher. Furthermore, the endothermic peak temperature is preferably 350°C or lower.

[0137] The endothermic peak temperature is the temperature corresponding to the minimum point in the heat of fusion curve obtained by differential scanning calorimetry (DSC) of a fluororesin that has not been heated to a temperature of 300°C or higher at a heating rate of 10°C / min. If two or more minimum points exist in a single melting peak, each of these minimum points shall be regarded as the endothermic peak temperature.

[0138] The TFE-based polymer exhibits one or more endothermic peaks in the range of 333 to 347°C in a heat of fusion curve when heated at a rate of 10°C / min using a differential scanning calorimeter [DSC]. The heat of fusion at 290 to 350°C calculated from the heat of fusion curve is preferably 62 mJ / mg or more.

[0139] From the perspective of forming a composite sheet with higher strength, the number average molecular weight (Mn) of the TFE polymer is preferably 0.5×10 6 More than 1.0×10 6 More preferably, 1.5×10 6 More than 2.0×10 6 More than 3.0×10 6 In addition, the number average molecular weight is preferably 20.0×10 6 less than 15.0×10 6 Below, more preferably 12.0×10 6 less than 10.0×10 6 Below, particularly preferably 8.0×10 6 the following.

[0140] The number average molecular weight is determined by estimating the heat of crystallization by measuring the temperature drop of a molten fluororesin using a differential scanning calorimeter (DSC) according to the method described in the following literature. The measurement was performed five times, and the average of the three values, excluding the maximum and minimum values, was used.

[0141] Literature: Suwa, T.; Takehisa, M.; Machi, S., J.Appl.Polym.Sci.vol.17, pp.3253(1973).

[0142] The content of the TFE polymer in the TFE polymer composition of the present invention may 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, relative to the TFE polymer composition.

[0143] The TFE-based polymer composition of the present invention preferably contains substantially no water. This can further suppress degradation of battery characteristics and improve composite sheet strength. Furthermore, a wide range of electrode active materials and solid electrolytes can be selected for combination, thus facilitating production processes. "Substantially no water" means a water content of 0.050% by mass or less relative to the TFE-based polymer composition.

[0144] The water content is preferably 0.040 mass% or less, more preferably 0.020 mass% or less, further preferably 0.010 mass% or less, still more preferably 0.005 mass% or less, and particularly preferably 0.002 mass% or less.

[0145] The above-mentioned water content is measured by the following method.

[0146] The mass of the TFE polymer composition was measured before and after heating at 150°C for 2 hours, and the mass was calculated according to the following formula: 3 samples were taken, the mass was calculated for each sample, and the average value was calculated and used.

[0147] Water content (mass %) = [(mass of the TFE polymer composition before heating (g)) - (mass of the TFE polymer composition after heating (g))] / (mass of the TFE polymer composition before heating (g)) × 100

[0148] The TFE polymer composition of the present invention preferably contains substantially no fluorinated compounds having a molecular weight of 1000 or less (excluding compounds (1) and (2) described above). Substantially containing no fluorinated compounds means that the amount of the fluorinated compounds is 25 ppb by mass or less relative to the TFE polymer composition.

[0149] The amount of the fluorinated compound is preferably less than 25 ppb by mass, more preferably 10 ppb by mass or less, further preferably less than 10 ppb by mass, even more preferably 5 ppb by mass or less, even more preferably 3 ppb by mass or less, even more preferably 1 ppb by mass or less, and particularly preferably less than 1 ppb by mass. The lower limit is not particularly limited, and the amount may be less than the quantitative lower limit.

[0150] The amount of the fluorine-containing compound having a molecular weight of 1000 or less is measured by the following method.

[0151] Weigh 1 g of the sample, add 10 g (12.6 ml) of methanol, and perform ultrasonic treatment for 60 minutes to obtain an extract. The obtained extract is appropriately concentrated by purging with nitrogen, and the fluorine-containing compounds in the concentrated extract are determined by LC / MS / MS. The molecular weight information is selected from the obtained LC / MS spectrum, and it is confirmed that it is consistent with the structural formula of the candidate fluorine-containing compound. Aqueous solutions with more than 5 levels of the standard substance are prepared, and LC / MS analysis of the aqueous solutions with each content is performed. The relationship between the content and the area of ​​the region relative to the content is plotted to draw a calibration curve. Using the above calibration curve, the area of ​​the LC / MS chromatogram of the fluorine-containing compound in the extract is converted into the content of the fluorine-containing compound.

[0152] It should be noted that the lower limit of quantification in this measurement method is 10 mass ppb.

[0153] The amount of the fluorine-containing compound having a molecular weight of 1000 or less can also be measured by the following method.

[0154] Weigh 1 g of the sample, add 10 g (12.6 ml) of methanol, perform ultrasonic treatment at 60°C for 2 hours, let it stand at room temperature, remove the solid components, and obtain an extract. The obtained extract is appropriately purged with nitrogen for concentration, and the fluorine-containing compounds in the concentrated extract are determined by LC / MS / MS. The molecular weight information is selected from the obtained LC / MS spectrum, and it is confirmed that it is consistent with the structural formula of the candidate fluorine-containing compound. Prepare 5 levels of methanol standard solutions of fluorine-containing compounds with known concentrations, and measure them using a liquid chromatography-mass spectrometer. In each concentration range, a calibration curve is prepared using a first-order approximation from the concentration of the methanol standard solution and the integral value of the peak. The content of the fluorine-containing compound contained in the extract is determined by the above calibration curve, and the content of the fluorine-containing compound contained in the sample is converted.

[0155] It should be noted that the lower limit of quantification in this measurement method is 1 mass ppb.

[0156] Examples of the fluorine-containing compound having a molecular weight of 1000 or less include fluorine-containing compounds having a molecular weight of 1000 g / mol or less and having a hydrophilic group. The molecular weight of the fluorine-containing compound is preferably 800 or less, more preferably 500 or less.

[0157] The polymerized particles obtained by polymerization in the presence of a fluorinated surfactant generally contain a fluorinated surfactant in addition to the TFE-based polymer. In this specification, the fluorinated surfactant is used during polymerization.

[0158] The fluorine-containing compound having a molecular weight of 1000 or less may be a compound not added during polymerization, for example, a compound produced as a by-product during polymerization.

[0159] It should be noted that the fluorinated compound having a molecular weight of 1000 or less, when comprising an anionic portion and a cationic portion, refers to a fluorinated compound having an anionic portion with a molecular weight of 1000 or less. The fluorinated compound having a molecular weight of 1000 or less does not include TFE-based polymers.

[0160] As the hydrophilic group, for example, -COOM, -SO2M or -SO3M can be mentioned, and -COOM, -SO3M (wherein M is H, metal atom, NR 1 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 1is an anionic group such as H or an organic group (preferably an organic group not containing fluorine).

[0161] As the above-mentioned fluorine-containing surfactant, a surfactant containing fluorine (anionic fluorine-containing surfactant) whose anionic portion has a molecular weight of 1000 or less can also be used. The above-mentioned "anionic portion" refers to the portion of the above-mentioned fluorine-containing surfactant other than the cation. For example, in F(CF2) n1 In the case of COOM, it is "F(CF2) n1 COO” part.

[0162] Examples of the anionic fluorinated surfactant include the following general formula (N 0 ):

[0163] X n0 -Rf n0 -Y 0 (N 0 )

[0164] (Where X n0 For H, Cl or and F. Rf n0 It is a chain, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H groups are replaced by F. The alkylene group may contain one or more ether bonds, and some of the H groups may be replaced by Cl. 0 is an anionic group).

[0165] Y 0 The anionic group may be -COOM, -SO2M or -SO3M, or may be -COOM or -SO3M.

[0166] M is H, metal atom, NR 1 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 1 is H or an organic group.

[0167] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, and Li.

[0168] As R 1 , which can be H or C 1-10 The organic group can be H or C 1-4 The organic group can also be H or C 1-4 of alkyl.

[0169] M can be H, metal atom or NR 1 4, can be H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 14, can also be H, Na, K, Li or NH4.

[0170] The above Rf n0 In the present invention, more than 50% of the H can be replaced by fluorine.

[0171] The fluorinated surfactant may be a single fluorinated surfactant or a mixture of two or more fluorinated surfactants.

[0172] Examples of the fluorinated surfactant include compounds represented by the following formulas: The fluorinated surfactant may be a mixture of these compounds.

[0173] F(CF2)7COOM,

[0174] F(CF2)5COOM,

[0175] CF3O(CF2)3OCHFCF2COOM,

[0176] C3F7OCF(CF3)CF2OCF(CF3)COOM,

[0177] CF3CF2CF2OCF(CF3)COOM,

[0178] CF3CF2OCF2CF2OCF2COOM,

[0179] C2F5OCF(CF3)CF2OCF(CF3)COOM,

[0180] CF3OCF(CF3)CF2OCF(CF3)COOM,

[0181] CF2ClCF2CF2OCF(CF3)CF2OCF2COOM,

[0182] CF2ClCF2CF2OCF2CF(CF3)OCF2COOM,

[0183] CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM,

[0184] CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, and

[0185] [Chemistry 3]

[0186]

[0187] (In each formula, M is H, metal atom, NR 14. An imidazolium which may have a substituent group, a pyridinium which may have a substituent group, or a phosphonium which may have a substituent group. 1 is H or an organic group. ).

[0188] The TFE-based polymer composition of the present invention preferably contains substantially no fluorinated compounds represented by the above formula.

[0189] In the above formulas, M can be H, a metal atom or NR 1 4, can be H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 1 4, can also be H, Na, K, Li or NH4.

[0190] R 1 Can be H or C 1-10 The organic group can be H or C 1-4 The organic group can also be H or C 1-4 of alkyl.

[0191] When the TFE-based polymer composition of the present invention does not substantially contain any of the fluorine-containing compounds represented by the above formula, degradation of battery characteristics can be further suppressed and the strength of the composite sheet can be further improved.

[0192] The phrase "substantially not containing any of the fluorinated compounds represented by the above formula" means that the amount of the fluorinated compound is 25 ppb by mass or less based on the TFE-based polymer composition.

[0193] The amount of the fluorinated compound is preferably less than 25 ppb by mass, more preferably 10 ppb by mass or less, further preferably less than 10 ppb by mass, even more preferably 5 ppb by mass or less, even more preferably 3 ppb by mass or less, even more preferably 1 ppb by mass or less, and particularly preferably less than 1 ppb by mass. The lower limit is not particularly limited, and the amount may be less than the quantitative lower limit.

[0194] The TFE-based polymer composition of the present invention also preferably does not substantially contain the following general formula:

[0195] [C n-1 F 2n-1 COO - ]M +

[0196] (wherein, n represents an integer of 9 to 14, preferably an integer of 9 to 12, and M + This can further suppress the degradation of battery characteristics and further improve the strength of the composite sheet.

[0197] The cation M in the above formula +The M is the same as the M mentioned above.

[0198] The phrase "substantially containing no fluorine-containing compound represented by the above formula" means that the amount of the fluorine-containing compound is 25 ppb by mass or less based on the TFE-based polymer composition.

[0199] The amount of the fluorinated compound is preferably less than 25 ppb by mass, more preferably 10 ppb by mass or less, further preferably less than 10 ppb by mass, even more preferably 5 ppb by mass or less, even more preferably 3 ppb by mass or less, even more preferably 1 ppb by mass or less, and particularly preferably less than 1 ppb by mass. The lower limit is not particularly limited, and the amount may be less than the quantitative lower limit.

[0200] The TFE-based polymer composition of the present invention preferably has non-melt secondary processability. This non-melt secondary processability refers to the property that the melt flow rate cannot be measured at temperatures above the melting point according to ASTM D-1238 and D-2116. In other words, it refers to the property of not being able to flow easily even in the melting temperature range.

[0201] The 0.1% mass loss temperature of the TFE polymer compositions (1), (3), (4), and (6) of the present invention may be 400°C or lower. The 0.1% mass loss temperature of the TFE polymer compositions (2) and (5) of the present invention is 400°C or lower.

[0202] A TFE-based polymer composition having a 0.1% mass loss temperature of 400° C. or lower is obtained by using a hydrocarbon-based surfactant.

[0203] The 0.1% mass loss temperature may be 350° C. or higher.

[0204] The 0.1% mass loss temperature is a value measured by the following method.

[0205] Approximately 10 mg of a TFE-based polymer composition that has not been heated to a temperature of 300°C or higher was accurately weighed and placed in a dedicated aluminum pan for TG-DTA (differential thermal analysis and thermogravimetric analysis). The 0.1% mass loss temperature was determined by heating the aluminum pan at a rate of 10°C / minute over a temperature range from 25°C to 600°C in an atmosphere. The temperature corresponding to a 0.1% mass loss was determined as the temperature at which the weight decreased by 0.1% by mass.

[0206] The 1.0% mass loss temperature of the TFE polymer compositions (1), (2), (4), and (5) of the present invention can be 492°C or lower. The 1.0% mass loss temperature of the TFE polymer compositions (3) and (6) of the present invention is 492°C or lower.

[0207] A TFE-based polymer composition having a 1.0% mass loss temperature of 492° C. or lower is obtained by using a hydrocarbon-based surfactant.

[0208] The 1.0% mass loss temperature may be 400° C. or higher, 420° C. or higher, 450° C. or higher, or 470° C. or higher.

[0209] The 1.0% mass loss temperature is a value measured by the following method.

[0210] Approximately 10 mg of a TFE-based polymer composition that has not been heated to a temperature of 300°C or higher was accurately weighed and placed in a dedicated aluminum pan for TG-DTA (differential thermal analysis and thermogravimetric analysis). The 1.0% mass loss temperature was determined by heating the aluminum pan at a rate of 10°C / minute over a temperature range from 25°C to 600°C in an atmosphere. The 1.0% mass loss temperature corresponded to the point at which the weight decreased by 1.0% by mass.

[0211] The TII of the TFE polymer compositions (1) to (3), (5) and (6) of the present invention is preferably not less than 20. The thermal instability index (TII) of the TFE polymer composition (4) of the present invention is not less than 20.

[0212] A TFE polymer composition having a TII of 20 or greater is obtained by using a hydrocarbon-based surfactant. The TII is preferably 25 or greater, more preferably 30 or greater, further preferably 35 or greater, and particularly preferably 40 or greater. Furthermore, the TII is preferably 50 or less.

[0213] The TII is measured in accordance with ASTM D 4895-89.

[0214] The TFE polymer compositions (1), (5), and (6) of the present invention are preferably stretchable. The TFE polymer compositions (2) to (4) of the present invention are stretchable. If they are stretchable, the strength of the composite sheet is further improved.

[0215] Being able to stretch means that a stretched body can be obtained in the following tensile test.

[0216] The strips obtained by extruding the paste under the above-mentioned RR100 are heated at 230°C for 30 minutes to remove the lubricant from the strips. Next, the strips (extruded products) are cut into appropriate lengths, each end is fixed to the chucks in such a way that the chucks are spaced 1.5 inches (38 mm) apart, and heated to 300°C in an air circulating oven. Next, the chucks are separated at the desired speed (stretching speed) to a separation distance corresponding to the desired stretching (total stretching) and a stretching test (stretching test) is carried out. This stretching method is essentially the method disclosed in the specification of U.S. Patent No. 4,576,869, except that the extrusion speed is different (51 cm / min instead of 84 cm / min). "Stretching" refers to the increase in length caused by extension, usually expressed as a ratio relative to the original length. In the stretching method, the stretching speed is 1000% / second and the above-mentioned total stretching is 2400%.

[0217] The SSG of the TFE polymer compositions (1) to (4) of the present invention is preferably 2.200 or less. The standard specific gravity (SSG) of the TFE polymer compositions (5) and (6) of the present invention is 2.200 or less. When the SSG is 2.200 or less, the deterioration of battery characteristics can be further suppressed, and the stretchability, adhesive strength, strength, and flexibility of the composite sheet can be improved.

[0218] The SSG is more preferably 2.190 or less, further preferably 2.180 or less, still more preferably 2.175 or less, particularly preferably 2.170 or less, and particularly preferably 2.165 or less.

[0219] Furthermore, the SSG is preferably 2.130 or greater.

[0220] The SSG is measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895.

[0221] From the perspective of further suppressing the deterioration of battery characteristics and improving the adhesive force, strength and flexibility of the composite sheet, the extrusion pressure of the TFE-based polymer composition of the present invention at a compression ratio (RR) of 100 is preferably 10 MPa or more, more preferably 12 MPa or more, further preferably 15 MPa or more, still more preferably 16 MPa or more, and particularly preferably 17 MPa or more.

[0222] In addition, from the perspective of improving processability, the extrusion pressure at RR100 is preferably 50 MPa or less, more preferably 40 MPa or less, further preferably 35 MPa or less, even more preferably 30 MPa or less, even more preferably 25 MPa or less, and particularly preferably 20 MPa or less.

[0223] The extrusion pressure at RR100 was determined by the following method based on the method described in Japanese Patent Application Laid-Open No. 2002-201217.

[0224] 21.7 g of lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon) was added to 100 g of TFE-based polymer composition and mixed in a glass bottle at room temperature for 3 minutes. Then, the glass bottle was placed at room temperature (25°C) for at least 1 hour before extrusion to obtain a lubricated resin. The lubricated resin was passed through a hole (diameter 2.5 mm, land length 11 mm, introduction angle 30°) and paste extruded at room temperature at a reduction ratio of 100:1 to obtain a uniform beading (extruded molded body). The extrusion speed, that is, the punch speed, was set to 20 inches / minute (51 cm / minute). During paste extrusion, the load when the extrusion load reaches a balanced state was measured and divided by the cross-sectional area of ​​the barrel used for paste extrusion to calculate the extrusion pressure.

[0225] From the perspective of being able to further suppress the deterioration of battery characteristics and from the perspective of improving the adhesive force, strength and flexibility of the composite sheet, the extrusion pressure of the TFE-based polymer composition of the present invention at RR300 is preferably 18 MPa or more, more preferably 23 MPa or more, further preferably 25 MPa or more, even more preferably 28 MPa or more, especially preferably 30 MPa or more, and particularly preferably 32 MPa or more.

[0226] In addition, from the viewpoint of improving processability, the extrusion pressure at RR300 is preferably 45 MPa or less, more preferably 40 MPa or less.

[0227] The extrusion pressure at RR300 is measured by the following method.

[0228] 50 g of a TFE-based polymer composition and 11.00 g of a hydrocarbon oil (trade name: Isopar E, manufactured by ExxonMobil) as an extrusion aid were mixed in a polyethylene container for 3 minutes. At room temperature (25°C), the mixture was filled into the barrel of the extruder, and a load of 0.47 MPa was applied to the piston inserted into the barrel and maintained for 1 minute. Next, the extruder was extruded from the hole at a punching speed of 18 mm / min. The ratio of the cross-sectional area of ​​the barrel to the cross-sectional area of ​​the hole (compression ratio) was 300. In the second half of the extrusion operation, the value obtained by dividing the load (N) when the pressure reaches equilibrium by the cross-sectional area of ​​the barrel was used as the extrusion pressure (MPa).

[0229] From the perspective of further suppressing the degradation of battery characteristics and improving the adhesive force, strength, and flexibility of the composite sheet, the breaking strength of the TFE-based polymer composition of the present invention is preferably 10.0 N or more, more preferably 13.0 N or more, even more preferably 16.0 N or more, even more preferably 19.0 N or more, even more preferably 22.0 N or more, even more preferably 25.0 N or more, even more preferably 28.0 N or more, even more preferably 30.0 N or more, even more preferably 32.0 N or more, and particularly preferably 35.0 N or more. The higher the breaking strength, the better, and it can be 100.0 N or less, 80.0 N or less, or 50.0 N or less.

[0230] The above-mentioned breaking strength is a value obtained by the following method.

[0231] The tensile bar obtained in the above tensile test (made by stretching a bar) was clamped and fixed in movable jaws with a gauge length of 5.0 cm, and a tensile test was performed at 25°C and a speed of 300 mm / min. The strength at break was measured as the breaking strength.

[0232] The TFE polymer composition of the present invention is preferably stretchable up to 24 times in order to further suppress degradation of battery characteristics and further improve adhesive strength, strength, and flexibility of the mixture sheet.

[0233] Being able to be stretched up to 24 times means that the material does not break during the stretching in the above-mentioned tensile test.

[0234] The form of the TFE-based polymer composition of the present invention is not limited, but is preferably a powder from the viewpoint of being able to be mixed with an electrode active material and a solid electrolyte without using a large amount of a dispersion medium.

[0235] It should be noted that the TFE-based polymer composition may be in a form other than powder, for example, a dispersion.

[0236] The average primary particle size of the TFE polymer composition of the present invention is preferably 100 to 500 nm. By setting the average primary particle size within this range, the molecular weight of the TFE polymer is increased, and the adhesive strength and flexibility of the composite sheet are improved.

[0237] The above-mentioned average primary particle size is more preferably 400 nm or less, further preferably 350 nm or less, still more preferably 330 nm or less, still more preferably 320 nm or less, still more preferably 300 nm or less, still more preferably 280 nm or less, and particularly preferably 250 nm or less. In addition, it is more preferably 150 nm or more, further preferably 170 nm or more, and still more preferably 200 nm or more.

[0238] The above-mentioned average primary particle size is measured by the following method.

[0239] A TFE polymer aqueous dispersion was diluted with water to a solids concentration of 0.15% by mass. The transmittance per unit length of the resulting diluted emulsion at 550 nm was measured, along with the number-based length-average primary particle size determined by measuring the orientation diameter using a transmission electron microscope photograph. A calibration curve was created. The average primary particle size was determined from the measured transmittance of each sample at 550 nm using this calibration curve.

[0240] Alternatively, the average primary particle size can be measured using dynamic light scattering. For this method, an aqueous TFE polymer dispersion adjusted to a solids concentration of approximately 1.0% by mass is prepared and measured using an ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) at 25°C for 70 cumulative measurements. The refractive index of the solvent (water) is 1.3328, and the viscosity of the solvent (water) is 0.8878 mPa·s.

[0241] The average secondary particle size of the TFE-based polymer composition of the present invention can be 350 μm or more, preferably 400 μm or more, more preferably 450 μm or more, further preferably 500 μm or more, even more preferably 550 μm or more, and particularly preferably 600 μm or more. In addition, it is preferably 1000 μm or less, more preferably 900 μm or less, further preferably 800 μm or less, and even more preferably 700 μm or less.

[0242] The above-mentioned average secondary particle size is measured in accordance with JIS K 6891.

[0243] From the perspective of excellent workability, the average aspect ratio of the TFE polymer composition of the present invention may be 2.0 or less, preferably 1.8 or less, more preferably 1.7 or less, even more preferably 1.6 or less, still more preferably 1.5 or less, still more preferably 1.4 or less, particularly preferably 1.3 or less, particularly preferably 1.2 or less, and most preferably 1.1 or less. Furthermore, the average aspect ratio may be 1.0 or greater.

[0244] The above-mentioned average aspect ratio is obtained by observing a TFE-based polymer composition or an aqueous dispersion of a TFE-based polymer diluted to a solid content concentration of about 1% by mass using a scanning electron microscope (SEM), performing image processing on more than 200 randomly selected particles, and calculating the average ratio of their major diameter to minor diameter.

[0245] From the perspective of obtaining a composite sheet having good moldability and high breaking strength, the TFE polymer composition of the present invention preferably contains fibrous particles having an aspect ratio of 1.5 or greater at a ratio of 20 to 60% relative to all TFE polymer particles.

[0246] The ratio of the fibrous particles to all particles can be calculated as follows.

[0247] (1) The TFE polymer powder containing the fibrous particles is imaged using a scanning electron microscope (SEM). The imaging magnification may be, for example, 300 to 1000 times.

[0248] (2) The video images are input into a computer, and image analysis software such as ImageJ is used to classify all particles into the above-mentioned fibrous particles and particles with an aspect ratio of less than 1.5.

[0249] (3) The number of the fibrous particles is divided by the total number of particles, that is, the total number of the fibrous particles and particles with an aspect ratio of less than 1.5, to calculate the ratio of the fibrous particles to the total number of particles.

[0250] The fibrous particles having an aspect ratio of 1.5 or greater are formed, for example, when the TFE-based polymer composition is mixed with an electrode active material and a solid electrolyte.

[0251] From the perspective of excellent workability, the apparent density of the TFE-based polymer composition of the present invention is preferably 0.40 g / ml or greater, more preferably 0.43 g / ml or greater, even more preferably 0.45 g / ml or greater, still more preferably 0.48 g / ml or greater, and particularly preferably 0.50 g / ml or greater. The upper limit is not particularly limited and may be 0.70 g / ml.

[0252] The above apparent density is measured in accordance with JIS K 6892.

[0253] The TFE-based polymer composition of the present invention can be suitably produced, for example, by a production method comprising the steps of (A) obtaining an aqueous dispersion of the TFE-based polymer by emulsion polymerization using a hydrocarbon-based surfactant, (B) precipitating the aqueous dispersion to obtain a wet powder, and (C) drying (heat-treating) the wet powder.

[0254] In the above hydrocarbon surfactant, the ratio of hydrogen atoms bonded to carbon atoms to be substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0255] The hydrocarbon surfactant is preferably a carboxylic acid hydrocarbon surfactant. The carboxylic acid hydrocarbon surfactant is not limited as long as it has a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.). For example, the specific hydrocarbon surfactants described below and hydrocarbon surfactants having a carboxyl group or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation in other compounds having surface activity can be used.

[0256] The hydrocarbon surfactant is also preferably a sulfonic acid type hydrocarbon surfactant. The sulfonic acid type hydrocarbon surfactant is not limited as long as it has a -SO3H group, -OSO3H group, or a group in which the hydrogen atoms of these groups are substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.). For example, the specific hydrocarbon surfactants described below and hydrocarbon surfactants having -SO3H group, -OSO3H group, or a group in which the hydrogen atoms of these groups are substituted with an inorganic cation in other compounds having surface activity can be used.

[0257] From the perspective of good emulsification performance, the hydrocarbon surfactant is preferably water-soluble. Water-soluble hydrocarbon surfactants mean that the maximum concentration at which the hydrocarbon surfactant dissolves in water at 85°C is 100 ppm by mass or higher. The maximum concentration at which the hydrocarbon surfactant dissolves in water is preferably 500 ppm by mass or higher, more preferably 1000 ppm by mass or higher, even more preferably 2000 ppm by mass or higher, even more preferably 3000 ppm by mass or higher, even more preferably 5000 ppm by mass or higher, even more preferably 1% by mass or higher, even more preferably 3% by mass or higher, even more preferably 5% by mass or higher, and particularly preferably 10% by mass or higher. Alternatively, the maximum concentration may be 50% by mass or lower.

[0258] Step (A) preferably includes the steps of emulsion polymerization of tetrafluoroethylene alone, or emulsion polymerization of tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene, in an aqueous medium in the presence of a specific hydrocarbon-based surfactant, and continuously adding the specific hydrocarbon-based surfactant during the above steps.

[0259] Continuously adding a specific hydrocarbon-based surfactant means, for example, not adding the specific hydrocarbon-based surfactant all at once, but adding it over time without interruption or division. The specific hydrocarbon-based surfactant is, for example, a hydrocarbon-based surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon-based surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) subjected to a free radical treatment or oxidation treatment. The above-mentioned free radical treatment can be any treatment that generates free radicals in a hydrocarbon-based surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), for example, the following treatment: adding deionized water and a hydrocarbon-based surfactant to a reactor, sealing the reactor, replacing the system with nitrogen, raising the temperature and pressure of the reactor, adding a polymerization initiator, stirring for a certain period of time, depressurizing until the reactor reaches atmospheric pressure, and cooling. The above-mentioned oxidation treatment is a treatment in which an oxidant is added to a hydrocarbon-based surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). As the oxidizing agent, for example, oxygen, ozone, hydrogen peroxide, manganese (IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, etc. By the above-mentioned production method, even without using an existing fluorinated surfactant, a TFE-based polymer having a molecular weight equivalent to that of a production method using an existing fluorinated surfactant can be produced.

[0260] In the above-mentioned production method, the step of continuously adding the specific hydrocarbon-based surfactant to the aqueous medium preferably begins when the solids content of the TFE-based polymer formed in the aqueous medium is less than 0.60% by mass. Preferably, the addition of the specific hydrocarbon-based surfactant to the aqueous medium begins when the solids content is 0.5% by mass or less. More preferably, the addition of the specific hydrocarbon-based surfactant begins when the solids content is 0.3% by mass or less, further preferably when it is 0.2% by mass or less, even more preferably when it is 0.1% by mass or less, and particularly preferably, when polymerization begins. The above-mentioned solids content refers to the concentration relative to the total of the aqueous medium and the TFE-based polymer.

[0261] In the step of continuously adding the specific hydrocarbon-based surfactant, the amount of the specific hydrocarbon-based surfactant added is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium. The more preferred lower limit is 0.05% by mass, the further preferred lower limit is 0.1% by mass, and the more preferred upper limit is 5% by mass, the further preferred upper limit is 1% by mass.

[0262] In the presence of the above-mentioned specific hydrocarbon surfactant, in the process of emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the above-mentioned tetrafluoroethylene in an aqueous medium, the amount of the above-mentioned specific hydrocarbon surfactant is preferably large, preferably 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferred lower limit is 0.001% by mass, and a more preferred upper limit is 1% by mass. When it is less than 0.0001% by mass, the dispersion force may be insufficient. When it is greater than 10% by mass, an effect commensurate with the amount is obtained, which may cause a decrease in the polymerization rate or cessation of the reaction. The amount of the above-mentioned specific hydrocarbon surfactant is appropriately determined according to the type of monomer used, the molecular weight of the target TFE polymer, etc.

[0263] As the above-mentioned specific hydrocarbon surfactant, it is preferably selected from the formula: RX (wherein, R is a non-fluorinated organic group having 1 to 2000 carbon atoms and having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), and X is -OSO3X 1 、-COOX 1 or -SO3X 1 (X 1 H, metal atoms, NR 1 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 1 R is H or an organic group (preferably a fluorine-free organic group), and may be the same or different. It is at least one of the surfactants shown in (a) and the surfactant (e) described below. R preferably has 500 or less carbon atoms, more preferably 100 or less, even more preferably 50 or less, and even more preferably 30 or less.

[0264] As the above-mentioned specific hydrocarbon-based surfactant, it is more preferable to be selected from the following formula (a):

[0265] [Chemistry 4]

[0266]

[0267] (Where R 1a It is a linear 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 may be substituted by hydroxyl groups or monovalent organic groups containing ester bonds (preferably organic groups not containing fluorine). When the number of carbon atoms is 2 or more, it may contain a carbonyl group. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. 2a and R 3a R is independently a single bond or a divalent linking group. 1a 、R 2a and R 3aThe total number of carbon atoms is 6 or more. a H, metal atoms, NR 4a 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 4a R is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. 1a 、R 2a and R 3a Any two of them can be bonded to each other to form a ring) represented by the surfactant (a), the following formula (b):

[0268] [Chemistry 5]

[0269]

[0270] (Where R 1b It is a linear or branched alkyl group with 1 or more carbon atoms which may be substituted or an alkyl group with 3 or more carbon atoms which may be substituted or an alkyl group with 3 or more carbon atoms. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring. 2b and R 4b R is independently H or a substituent. 3b is an alkylene group having 1 to 10 carbon atoms which may be substituted. n is an integer greater than 1. p and q are independently an integer greater than 0. b H, metal atoms, NR 5b 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5b R is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. 1b 、R 2b 、R 3b and R 4b Any two of them can be bonded to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*、-NR 6b CO-B-*, or -CO-(wherein -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 CO-B-excluding carbonyl groups), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6b It is H or an alkyl group with 1 to 4 carbon atoms which may have a substituent. * refers to -OSO3X in the formula b The surfactant (b) shown in the following formula (c):

[0271] [Chemistry 6]

[0272]

[0273] (Where R 1c It is a linear 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 may be substituted by hydroxyl groups or monovalent organic groups containing ester bonds (preferably organic groups not containing fluorine). When the number of carbon atoms is 2 or more, it may contain a carbonyl group. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. 2c and R 3c R is independently a single bond or a divalent linking group. 1c 、R 2c and R 3c The total number of carbon atoms in A is 5 or more. c COOX c or -SO3X c (X c H, metal atoms, NR 4c 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 4c is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. ). R 1c 、R 2c and R 3c Any two of them can be bonded to each other to form a ring. ) represented by surfactant (c), the following formula (d):

[0274] [Chemistry 7]

[0275]

[0276] (Where R 1d It is a linear or branched alkyl group with 1 or more carbon atoms which may be substituted or an alkyl group with 3 or more carbon atoms which may be substituted or an alkyl group with 3 or more carbon atoms. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring. 2d and R 4d R is independently H or a substituent. 3d A is an alkylene group having 1 to 10 carbon atoms and may have a substituent. n is an integer greater than 1. p and q are independently an integer greater than 0. d -SO3X d or -COOX d (X d H, metal atoms, NR 5d4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5d is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. ). R 1d 、R 2d 、R 3d and R 4d Any two of them can be bonded to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*、-NR 6d CO-B-*, or -CO-(wherein -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-excluding carbonyl groups), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6d is H or an alkyl group with 1 to 4 carbon atoms which may be substituted. * refers to the d The surfactant (d) shown in FIG. , and the following formula (e):

[0277] [Chemistry 8]

[0278]

[0279] (Where R 1e ~R 5e represents H or a monovalent substituent, but R 1e and R 3e At least one of the following represents the general formula: -Y e -R 6e The group shown, R 2e and R 5e At least one of them represents the general formula: -X e -A e The group shown, or the general formula: -Y e -R 6e The groups shown.

[0280] In addition, X e The same or different in each occurrence, represents a divalent linking group or a bond;

[0281] A e Same or different in each occurrence, indicates -COOM e 、-SO3M e or-OSO3M e (M e H, metal atoms, NR 7e4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7e is H or an organic group (preferably an organic group not containing fluorine);

[0282] Y e The same or different in each occurrence represents a group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e -and-NR 8e The divalent linking group or bond in the group consisting of CO-, R 8e represents H or an organic group (preferably an organic group not containing fluorine);

[0283] R 6e The groups are the same or different in each occurrence and represent an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms.

[0284] R 1e ~R 5e Any two of them can be bonded to each other to form a ring. At least one of the group consisting of surfactants (e) shown in ).

[0285] The surfactant (a) will be described.

[0286] In formula (a), R 1a It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0287] When the number of carbon atoms in the alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be included between two carbon atoms. Furthermore, when the number of carbon atoms in the alkyl group is 2 or more, the carbonyl group may be included at the end of the alkyl group. In other words, acyl groups such as acetyl groups represented by CH3-C(=O)- are also included in the alkyl group.

[0288] In addition, when the number of carbon atoms in the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring and may form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred, such as a furan ring. 1a In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above-mentioned alkyl group.

[0289] It should be noted that, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0290] In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted with any functional group.

[0291] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 101a (Where R 101a is an alkyl group).

[0292] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0293] Where R 2a and R 3a are independently a single bond or a divalent linking group.

[0294] Preferred R 2a and R 3a Each of the groups is independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0295] Composition R 2a and R 3a The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0296] In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted with any functional group.

[0297] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 102a (Where R 102a is an alkyl group).

[0298] In the above-mentioned alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, and 25% or less may be substituted by halogen atoms. Preferably, the alkylene group is a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0299] R 1a 、R 2a and R 3a The total number of carbon atoms is 6 or more. The total number of carbon atoms is preferably 8 or more, more preferably 9 or more, further preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 15 or less.

[0300] R 1a 、R 2a and R 3a Any two of them can be bonded to each other to form a ring.

[0301] In formula (a), X a H, metal atoms, NR 4a 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 4a is H or an organic group (preferably an organic group without fluorine). 4a They can be the same or different. 4a The organic group in is preferably an alkyl group. 4a , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, further preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and preferably Na, K or Li.

[0302] As X a , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 4a 4, from the perspective of being easily soluble in water, H, Na, K, Li or NH4 is more preferred, from the perspective of being more soluble in water, Na, K or NH4 is further preferred, Na or NH4 is particularly preferred, and from the perspective of being easily removed, NH4 is most preferred. a In the case of NH 4 , the surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the TFE-based polymer or the final product.

[0303] As R 1a, preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms without a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms without a carbonyl group, a straight-chain or branched alkyl group having 2 to 45 carbon atoms containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms and containing a monovalent or divalent heterocycle.

[0304] In addition, as R 1a , more preferably the following formula:

[0305] [Chemistry 9]

[0306]

[0307] (where n 11a is an integer from 0 to 10, R 11a is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, R 12a It is an alkylene group having 0 to 3 carbon atoms. 11a When R is an integer of 2 to 10, 12a They may be the same or different.

[0308] As n 11a , preferably an integer of 0-5, more preferably an integer of 0-3, further preferably an integer of 1-3.

[0309] As R 11a The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0310] As R 11a In the above-mentioned alkyl group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted by any functional group.

[0311] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 103a (Where R 103a is an alkyl group).

[0312] As R 11a In the above-mentioned alkyl group, less than 75% of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkyl group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0313] R 12a It is an alkylene group having 0 to 3 carbon atoms, preferably 1 to 3 carbon atoms.

[0314] As R12a The above-mentioned alkylene group may be linear or branched.

[0315] As R 12a The above alkylene group preferably does not contain a carbonyl group. 12a , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0316] As R 12a In the above-mentioned alkylene group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted by any functional group.

[0317] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 104a (Where R 104a is an alkyl group).

[0318] As R 12a In the above-mentioned alkylene group, less than 75% of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkylene group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0319] As R 2a and R 3a , are independently preferably an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0320] As surfactant (a), the following surfactants can be exemplified. a As mentioned above.

[0321] [Chemistry 10]

[0322]

[0323] [Chemistry 11]

[0324]

[0325] [Chemistry 12]

[0326]

[0327] [Chemistry 13]

[0328]

[0329] [Chemistry 14]

[0330]

[0331] [Chemistry 15]

[0332]

[0333] [Chemistry 16]

[0334]

[0335] [Chemistry 17]

[0336]

[0337] The surfactant (a) can be produced by the production method described in, for example, International Publication No. 2020 / 022355.

[0338] Next, the surfactant (b) will be described.

[0339] In formula (b), R 1b It is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent.

[0340] When the number of carbon atoms in the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring and may form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred, such as a furan ring. 1b In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above-mentioned alkyl group.

[0341] In addition, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the above-mentioned heterocyclic ring.

[0342] For R 1b The substituents that the alkyl group may have are preferably halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, and particularly preferably methyl groups and ethyl groups.

[0343] As R 1b The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0344] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0345] The above-mentioned alkyl group preferably does not have any substituent.

[0346] As R 1b , preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent, more preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a substituent, even more preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms without a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), most preferably a methyl group (-CH3).

[0347] In formula (b), R 2b and R 4b are independently H or a substituent. 2b and R 4b They can be the same or different.

[0348] For R 2b and R 4b The substituents are preferably halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, and particularly preferably methyl groups and ethyl groups.

[0349] As R 2b and R 4b The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0350] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0351] The above-mentioned alkyl group preferably does not have any substituent.

[0352] For R 2b and R 4b The above-mentioned alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, more preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms without a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0353] As R 2b and R 4b, independently preferably H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched alkyl group having 1 to 3 carbon atoms and not having a substituent, further more preferably H, methyl (-CH3) or ethyl (-C2H5), and particularly preferably H.

[0354] In formula (b), R 3b It is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3b When there are two or more, they may be the same or different.

[0355] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0356] In the above-mentioned alkylene group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. It is preferably a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0357] The above-mentioned alkylene group preferably does not have any substituent.

[0358] As the above-mentioned alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted or a cyclic alkylene group having 3 to 10 carbon atoms which may be substituted or not, a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group is preferred, a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a substituent is more preferred, and a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylidene group (-CH(CH3)CH2-) or a propylene group (-C3H6-) is further preferred.

[0359] R 1b 、R 2b 、R 3b and R 4b Any two of them may be bonded to each other to form a ring, but preferably do not form a ring.

[0360] In formula (b), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, further preferably an integer of 5 to 25, and particularly preferably an integer of 5 to 9 or 11 to 25.

[0361] In formula (b), p and q are independently integers greater than 0. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0362] The total of n, p, and q is preferably an integer of 5 or greater. The total of n, p, and q is more preferably an integer of 8 or greater. In addition, the total 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.

[0363] In formula (b), X b H, metal atoms, NR 5b 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5b is H or an organic group (preferably an organic group without fluorine). 5b They can be the same or different. 5b The organic group in is preferably an alkyl group. 5b , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and preferably Na, K or Li. X b It can be a metal atom or NR 5b 4(R 5b as described above).

[0364] As X b , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 5b 4, from the perspective of being easily soluble in water, H, Na, K, Li or NH4 is more preferred, from the perspective of being more soluble in water, Na, K or NH4 is further preferred, Na or NH4 is particularly preferred, and from the perspective of being easily removed, NH4 is most preferred. b In the case of NH 4 , the surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the TFE-based polymer or the final product.

[0365] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*、-NR 6b CO-B-*, or -CO-(wherein -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 CO-B-excluding carbonyl groups), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6b is H or an alkyl group with 1 to 4 carbon atoms which may be substituted. More preferably, the alkylene group has 1 to 5 carbon atoms. 6 Is H or methyl. * refers to -OSO3X in the formulab Bonding side.

[0366] Preferably, L is a single bond.

[0367] As the surfactant (b), the following formula is preferred:

[0368] [Chemistry 18]

[0369]

[0370] (Where R 1b 、R 2b , L, n and X b As described above).

[0371] The above surfactant (b) is preferably 1 The integrated value of the total peak intensity observed in the chemical shift region of 2.0 to 5.0 ppm in the H-NMR spectrum is 10% or more.

[0372] The above surfactant (b) is preferably 1 The integrated value of the total peak intensity observed in the chemical shift region of 2.0 to 5.0 ppm in the H-NMR spectrum is within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0373] In the surfactant (b), the integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and even more preferably 70 or less.

[0374] The above integrated value was measured at room temperature using a deuterated water solvent, with the deuterated water concentration set at 4.79 ppm.

[0375] Examples of the surfactant (b) include:

[0376] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0377] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0378] CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0379] CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na,

[0380] CH3C(O)CH2CH2CH2CH2CH2OSO3Na,

[0381] <h2 style=";text-align:left;direction:ltr">CH3C(O)CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0382] <h2 style=";text-align:left;direction:ltr"> (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0383] <h2 style=";text-align:left;direction:ltr"> (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0384] <h2 style=";text-align:left;direction:ltr"> (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0385] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0386] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0387] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0388] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0389] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0390] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0391] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0392] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0393] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0394] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0395] <h2 style=";text-align:left;direction:ltr">CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0396] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0397] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0398] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0399] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0400] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0401] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0402] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0403] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0404] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0405] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0406] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0407] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0408] <h2 style=";text-align:left;direction:ltr">CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0409] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0410] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0411] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0412] <h2 style=";text-align:left;direction:ltr"> (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0413] <h2 style=";text-align:left;direction:ltr"> (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0414] <h2 style=";text-align:left;direction:ltr"> (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0415] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0416] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0417] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0418] <h2 style=";text-align:left;direction:ltr"> CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0419] <h2 style=";text-align:left;direction:ltr">CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0420] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0421] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0422] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0423] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0424] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0425] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0426] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0427] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0428] <h2 style=";text-align:left;direction:ltr"> CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0429] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4,

[0430] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, etc.

[0431] The surfactant (b) can be produced by the production method described in, for example, International Publication No. 2020 / 022355.

[0432] Next, the surfactant (c) will be described.

[0433] In formula (c), R 1c It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0434] When the number of carbon atoms in the alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be included between two carbon atoms. Furthermore, when the number of carbon atoms in the alkyl group is 2 or more, the carbonyl group may be included at the end of the alkyl group. In other words, acyl groups such as acetyl groups represented by CH3-C(=O)- are also included in the alkyl group.

[0435] In addition, when the number of carbon atoms in the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring and may form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred, such as a furan ring. 1c In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above-mentioned alkyl group.

[0436] It should be noted that, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0437] In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted with any functional group.

[0438] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 101c (Where R 101c is an alkyl group).

[0439] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0440] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group.

[0441] R 2c and R 3c Each of them is preferably independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0442] Composition R 2c and R 3c The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0443] In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted with any functional group.

[0444] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 102c (Where R 102c is an alkyl group).

[0445] In the above-mentioned alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, and 25% or less may be substituted by halogen atoms. Preferably, the alkylene group is a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0446] R 1c 、R 2c and R 3c The total number of carbon atoms is 5 or more. The total number of carbon atoms is preferably 7 or more, more preferably 9 or more, and is preferably 20 or less, more preferably 18 or less, and further preferably 15 or less.

[0447] R 1c 、R 2c and R 3c Any two of them can be bonded to each other to form a ring.

[0448] In formula (c), Ac COOX c or -SO3X c (X c H, metal atoms, NR 4c 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 4c is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. ) As R 4c The organic group in is preferably an alkyl group. 4c , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, further preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and preferably Na, K or Li.

[0449] As X c , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 4c 4, from the perspective of being easily soluble in water, H, Na, K, Li or NH4 is more preferred, from the perspective of being more soluble in water, Na, K or NH4 is further preferred, Na or NH4 is particularly preferred, and from the perspective of being easily removed, NH4 is most preferred. c In the case of NH 4 , the surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the TFE-based polymer or the final product.

[0450] As R 1c , preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms without a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms without a carbonyl group, a straight-chain or branched alkyl group having 2 to 45 carbon atoms containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms and containing a monovalent or divalent heterocycle.

[0451] In addition, as R 1c , more preferably the following formula:

[0452] [Chemistry 19]

[0453]

[0454] (where n 11c is an integer from 0 to 10, R 11c is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, R 12c It is an alkylene group having 0 to 3 carbon atoms. 11c When R is an integer of 2 to 10, 12cThey may be the same or different.

[0455] As n 11c , preferably an integer of 0-5, more preferably an integer of 0-3, further preferably an integer of 1-3.

[0456] As R 11c The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0457] As R 11c In the above-mentioned alkyl group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted by any functional group.

[0458] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 103c (Where R 103c is an alkyl group).

[0459] As R 11c In the above-mentioned alkyl group, less than 75% of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkyl group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0460] R 12c It is an alkylene group having 0 to 3 carbon atoms, preferably 1 to 3 carbon atoms.

[0461] As R 12c The above-mentioned alkylene group may be linear or branched.

[0462] As R 12c The above alkylene group preferably does not contain a carbonyl group. 12c , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0463] As R 12c In the above-mentioned alkylene group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond (preferably a fluorine-free organic group), but is preferably not substituted by any functional group.

[0464] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 104c (Where R 104c is an alkyl group).

[0465] As R 12cIn the above-mentioned alkylene group, less than 75% of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkylene group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0466] As R 2c and R 3c , are independently preferably an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0467] Examples of the surfactant (c) include the following surfactants. c As mentioned above.

[0468] [Chemistry 20]

[0469]

[0470] [Chemistry 21]

[0471]

[0472] [Chemistry 22]

[0473]

[0474] [Chemistry 23]

[0475]

[0476] [Chemistry 24]

[0477]

[0478] [Chemistry 25]

[0479]

[0480] [Chemistry 26]

[0481]

[0482] [Chemistry 27]

[0483]

[0484] The surfactant (c) can be produced by the production method described in, for example, International Publication No. 2020 / 022355.

[0485] Next, the surfactant (d) will be described.

[0486] In formula (d), R1d It is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent.

[0487] When the number of carbon atoms in the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring and may form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred, such as a furan ring. 1d In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above-mentioned alkyl group.

[0488] In addition, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the above-mentioned heterocyclic ring.

[0489] For R 1d The substituents that the alkyl group may have are preferably halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, and particularly preferably methyl groups and ethyl groups.

[0490] As R 1d The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0491] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0492] The above-mentioned alkyl group preferably does not have any substituent.

[0493] As R 1d , preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent, more preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a substituent, even more preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms without a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), most preferably a methyl group (-CH3).

[0494] In formula (d), R 2d and R 4d are independently H or a substituent. 2d and R 4d They can be the same or different.

[0495] For R 2d and R 4d The substituents are preferably halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, and particularly preferably methyl groups and ethyl groups.

[0496] As R 2d and R 4d The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0497] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0498] The above-mentioned alkyl group preferably does not have any substituent.

[0499] For R 2d and R 4d The above-mentioned alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, more preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms without a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0500] As R 2d and R 4d , independently preferably H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched alkyl group having 1 to 3 carbon atoms and not having a substituent, further more preferably H, methyl (-CH3) or ethyl (-C2H5), and particularly preferably H.

[0501] In formula (d), R 3d It is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3d When there are two or more, they may be the same or different.

[0502] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0503] In the above-mentioned alkylene group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. It is preferably a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0504] The above-mentioned alkylene group preferably does not have any substituent.

[0505] As the above-mentioned alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted or a cyclic alkylene group having 3 to 10 carbon atoms which may be substituted or not, a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group is preferred, a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a substituent is more preferred, and a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylidene group (-CH(CH3)CH2-) or a propylene group (-C3H6-) is further preferred.

[0506] R 1d 、R 2d 、R 3d and R 4d Any two of them can be bonded to each other to form a ring.

[0507] In formula (d), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and even more preferably an integer of 5 to 25.

[0508] In formula (d), p and q are independently an integer greater than 0. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0509] The total of n, p, and q is preferably an integer of 6 or greater. The total of n, p, and q is more preferably an integer of 8 or greater. In addition, the total 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.

[0510] In formula (d), A d -SO3X d or -COOX d (X d H, metal atoms, NR 5d 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5d is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. ) As R 5d The organic group in is preferably an alkyl group. 5d , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and preferably Na, K or Li. X d It can be a metal atom or NR 5d 4(R 5das described above).

[0511] As X d , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 5d 4, from the perspective of being easily soluble in water, H, Na, K, Li or NH4 is more preferred, from the perspective of being more soluble in water, Na, K or NH4 is further preferred, Na or NH4 is particularly preferred, and from the perspective of being easily removed, NH4 is most preferred. d In the case of NH 4 , the surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the TFE-based polymer or the final product.

[0512] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*、-NR 6d CO-B-*, or -CO-(wherein -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-excluding carbonyl groups), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6d is H or an alkyl group with 1 to 4 carbon atoms which may be substituted. More preferably, the alkylene group has 1 to 5 carbon atoms. 6d is H or methyl. * refers to the d Bonding side.

[0513] Preferably, L is a single bond.

[0514] The above surfactant is preferably 1 The integrated value of the total peak intensity observed in the chemical shift region of 2.0 to 5.0 ppm in the H-NMR spectrum is 10 or more.

[0515] The above surfactant is preferably 1 The integrated value of the total peak intensity observed in the chemical shift region of 2.0 to 5.0 ppm in the H-NMR spectrum is within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0516] In the above surfactants, the integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and even more preferably 70 or less.

[0517] The above integrated value was measured at room temperature using a deuterated water solvent, with the deuterated water concentration set at 4.79 ppm.

[0518] Examples of the surfactant (d) include:

[0519] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK、

[0520] CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa、

[0521] CH3C(O)CH2CH2CH2CH2CH2CH2COONa、

[0522] CH3C(O)CH2CH2CH2CH2CH2COONa、

[0523] CH3C(O)CH2CH2CH2CH2COONa、

[0524] CH3C(O)CH2CH2CH2COONa、

[0525] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa、

[0526] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa、

[0527] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、

[0528] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、

[0529] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、

[0530] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa、

[0531] CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa、

[0532] CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa、

[0533] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa、

[0534] CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa、

[0535] CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa、

[0536] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa、

[0537] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa、

[0538] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK、

[0539] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK、

[0540] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa、

[0541] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa、

[0542] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa、

[0543] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH、

[0544] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi,

[0545] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4、

[0546] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa、CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK、

[0547] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、

[0548] <h2 style=";text-align:left;direction:ltr">CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0549] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0550] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0551] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0552] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0553] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0554] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0555] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0556] <h2 style=";text-align:left;direction:ltr"> (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0557] <h2 style=";text-align:left;direction:ltr"> (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0558] <h2 style=";text-align:left;direction:ltr"> (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0559] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0560] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0561] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0562] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2CH2SO3Na、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0563] <h2 style=";text-align:left;direction:ltr"> CH3C(O)CH2CH2CH2CH2SO3Na、

[0564] CH3C(O)CH2CH2CH2SO3Na,

[0565] CH3C(O)CH2CH2SO3Na,

[0566] CH3C(O)CH2SO3Na,

[0567] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na,

[0568] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na,

[0569] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na,

[0570] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na,

[0571] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na,

[0572] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na,

[0573] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H,

[0574] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K,

[0575] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li,

[0576] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4,

[0577] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na etc.

[0578] Surface activation method (d) can be passed as an example in the country publication No. 2020 / 022355.

[0579] Next, the surfactant (e) will be described.

[0580] In formula (e), R 1e ~R 5e represents H or a monovalent substituent, wherein R 1e and R 3e At least one of the following represents the general formula: -Y e -R 6e The group shown, R 2e and R 5e At least one of them represents the general formula: -X e -A e The group shown, or the general formula: -Y e -R 6e The group shown. 1e ~R 5e Any two of them may be bonded to each other to form a ring.

[0581] For R 1e The substituents that the alkyl group may have are preferably halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, and particularly preferably methyl groups and ethyl groups.

[0582] As R 1e The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0583] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0584] The above-mentioned alkyl group preferably does not have any substituent.

[0585] As R 1e , preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent, more preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms without a substituent, even more preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms without a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), most preferably a methyl group (-CH3).

[0586] As a monovalent substituent, preferably the general formula: -Y e -R 6e The group shown, general formula: -X e-A e The group shown, -H, C with or without substituents 1-20 Alkyl, -NH2, -NHR 9e (R 9e is an organic group (preferably a fluorine-free organic group), -OH, -COOR 9e (R 9e is an organic group (preferably an organic group not containing fluorine) or -OR 9e (R 9e is an organic group (preferably an organic group not containing fluorine). The number of carbon atoms in the alkyl group is preferably 1 to 10.

[0587] As R 9e , preferably C 1-10 Alkyl or C 1-10 Alkylcarbonyl, more preferably C 1-4 Alkyl or C 1-4 of an alkylcarbonyl group.

[0588] Where, X e The same or different in each occurrence represents a divalent linking group or a bonding bond.

[0589] R 6e In the case where no carbonyl group, ester group, amide group or sulfonyl group is included, it is preferred that X e It is a divalent linking group containing at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0590] As X e , preferably comprising a compound selected from -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, -CONR 8e -and-NR 8e A divalent connecting group having at least one bond in the group consisting of CO-, C 1-10 Alkylene, or bond. 8e represents H or an organic group (preferably an organic group not containing fluorine).

[0591] As R 8e The organic group in is preferably an alkyl group. 8e , preferably H or C 1-10 An organic group, more preferably H or C 1-4 An organic group, preferably H or C 1-4 An alkyl group is more preferably H.

[0592] In formula (e), A e Same or different in each occurrence, indicates -COOM e 、-SO3Me or-OSO3M e (M e H, metal atoms, NR 7e 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7e is H or an organic group (preferably an organic group without fluorine). 7e They may be the same or different. ). In formula (e), A e For-COOM e It is one of the preferred methods.

[0593] As R 7e The organic group in is preferably an alkyl group. 7e , preferably H or C 1-10 An organic group, more preferably H or C 1-4 An organic group, preferably H or C 1-4 of alkyl.

[0594] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred.

[0595] As M e , preferably H, metal atom or NR 7e 4. More preferably, H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7e 4. H, Na, K, Li or NH4 is further preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0596] In formula (e), Y e The same or different in each occurrence represents a group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e -and-NR 8e The divalent linking group or bond in the group consisting of CO-, R 8e represents H or an organic group (preferably an organic group not containing fluorine).

[0597] As Y e , preferably selected from the group consisting of bonding bonds, -O-, -COO-, -OCO-, -CONR 8e -and-NR 8e The divalent linking group is more preferably a divalent linking group selected from the group consisting of -CO-, a bond, -COO- and -OCO-.

[0598] As R 8e The organic group in is preferably an alkyl group. 8e , preferably H or C1-10 An organic group, more preferably H or C 1-4 An organic group, preferably H or C 1-4 An alkyl group is more preferably H.

[0599] In formula (e), R 6e The same or different in each occurrence, represents an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms. 6e The organic group (preferably a fluorine-free organic group) preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

[0600] R 6e The alkyl group may contain one or more carbonyl groups, ester groups, amide groups and sulfonyl groups between carbon atoms, but not at the end of the alkyl group. 6e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkyl group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0601] As R 6e , preferably:

[0602] General formula: -R 10e -CO-R 11e The groups shown,

[0603] General formula: -R 10e -COO-R 11e The groups shown,

[0604] General formula: -R 11e The groups shown,

[0605] General formula: -R 10e -NR 8e CO-R 11e The group shown, or

[0606] General formula: -R 10e -CONR 8e -R 11e The groups shown

[0607] (Where R 8e R represents H or an organic group (preferably an organic group not containing fluorine). 10e Preferably, alkylene, R 11e is an alkyl group which may have a substituent).

[0608] As R 6e, more preferably the general formula: -R 10e -CO-R 11e The groups shown.

[0609] As R 8e The organic group in is preferably an alkyl group. 8e , preferably H or C 1-10 An organic group, more preferably H or C 1-4 An organic group, preferably H or C 1-4 An alkyl group is more preferably H.

[0610] R 10e The number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. 10e The number of carbon atoms in the alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 3-10.

[0611] R 11e The number of carbon atoms in the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10, still more preferably 1 to 8, particularly preferably 1 to 6, still more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. 11e The alkyl group of R is composed only of primary carbon, secondary carbon and tertiary carbon, and is particularly preferably composed only of primary carbon and secondary carbon. 11e , preferably methyl, ethyl, n-propyl, isopropyl, and most preferably methyl.

[0612] In formula (e), R 2e and R 5e At least one of them is of the general formula: -X e -A e The group shown, the A e For-COOM e It is also one of the preferred methods.

[0613] As the surfactant (e), preferably, the compound represented by the general formula (e-1), the compound represented by the general formula (e-2), or the compound represented by the general formula (e-3) is used, and more preferably, the compound represented by the general formula (e-1) or the compound represented by the general formula (e-2) is used.

[0614] [Chemistry 28]

[0615]

[0616] (Where R 3e ~R 6e 、X e 、Ae and Y e As mentioned above) general formula (e-2):

[0617] [Chemistry 29]

[0618]

[0619] (Where R 4e ~R 6e 、X e 、A e and Y e As mentioned above) general formula (e-3):

[0620] [Chemistry 30]

[0621]

[0622] (Where R 2e 、R 4e ~R 6e 、X e 、A e and Y e As described above) as the general formula: -X e -A e The group shown is preferably:

[0623] -COOM e 、

[0624] -R 12e COOM e 、

[0625] -SO3M e 、

[0626] -OSO3M e 、

[0627] -R 12e SO3M e 、

[0628] -R 12e OSO3M e 、

[0629] -OCO-R 12e -COOM e 、

[0630] -OCO-R 12e -SO3M e 、

[0631] -OCO-R 12e -OSO3M e 、

[0632] -COO-R 12e -COOM e 、

[0633] -COO-R 12e -SO3M e 、

[0634] -COO-R 12e -OSO3M e 、

[0635] -CONR 8e -R 12e -COOM e 、

[0636] -CONR 8e -R 12e -SO3M e 、

[0637] -CONR 8e -R 12e -OSO3M e 、

[0638] -NR 8e CO-R 12e -COOM e 、

[0639] -NR 8e CO-R 12e -SO3M e 、

[0640] -NR 8e CO-R 12e -OSO3M e 、

[0641] -OS(=O)2-R 12e -COOM e 、

[0642] -OS(=O)2-R 12e -SO3M e ,or

[0643] -OS(=O)2-R 12e -OSO3M e

[0644] (Where R 8e and M e As mentioned above. 12e C 1-10 alkylene. ).

[0645] The above R 12eIn the alkylene group, less than 75% of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkylene group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0646] As a general formula: -Y e -R 6e The group shown is preferably:

[0647] General formula: -R 10e -CO-R 11e The groups shown,

[0648] General formula: -OCO-R 10e -CO-R 11e The groups shown,

[0649] General formula: -COO-R 10e -CO-R 11e The groups shown,

[0650] General formula: -OCO-R 10e -COO-R 11e The groups shown,

[0651] General formula: -COO-R 11e The groups shown,

[0652] General formula: -NR 8e CO-R 10e -CO-R 11e The group shown, or

[0653] General formula: -CONR 8e -R 10e -NR 8e CO-R 11e The groups shown

[0654] (Where R 8e 、R 10e and R 11e As mentioned above. ).

[0655] In the formula, as R 4e and R 5e , independently preferably H or C 1-4 of alkyl.

[0656] The above R 4e and R 5e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkyl group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0657] As R in the general formula (e-1) 3e , preferably H or C with or without substituents 1-20 Alkyl, more preferably H or unsubstituted C 1-20 The alkyl group is more preferably H.

[0658] The above R 3e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkyl group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0659] As R in the general formula (e-3) 2e , preferably H, OH or C with or without substituents 1-20 Alkyl, more preferably H, OH or unsubstituted C 1-20 The alkyl group is more preferably H or OH.

[0660] The above R 2e In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the non-halogenated alkyl group does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0661] The surfactant (e) can be produced by a known production method.

[0662] The above-mentioned specific hydrocarbon surfactant is also preferably a carboxylic acid-type hydrocarbon surfactant. The above-mentioned carboxylic acid-type hydrocarbon surfactant is not limited as long as it has a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation (e.g., a metal atom, ammonium, etc.). For example, hydrocarbon surfactants having a carboxyl group or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation among the above-mentioned specific hydrocarbon surfactants can be used.

[0663] The carboxylic acid-type hydrocarbon surfactant preferably has a ratio of fluorine atoms replacing hydrogen atoms bonded to carbon atoms of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0664] As the above-mentioned carboxylic acid-type hydrocarbon surfactant, it is preferred to select at least one surfactant from the group consisting of the surfactant (c) represented by the above-mentioned formula (c) and the surfactant (d) represented by the above-mentioned formula (d) and have a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation (such as a metal atom, ammonium, etc.).

[0665] Furthermore, the above-mentioned specific hydrocarbon-based surfactant is preferably a sulfonic acid-type hydrocarbon-based surfactant. The above-mentioned sulfonic acid-type hydrocarbon-based surfactant is not limited as long as it has a -SO3H group, -OSO3H group, or a group in which the hydrogen atoms of these groups are substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.). For example, among the above-mentioned specific hydrocarbon-based surfactants, hydrocarbon-based surfactants having a -SO3H group, -OSO3H group, or a group in which the hydrogen atoms of these groups are substituted with an inorganic cation can be used.

[0666] The sulfonic acid type hydrocarbon surfactant preferably has a ratio of fluorine atoms replacing hydrogen atoms bonded to carbon atoms of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0667] The TFE-based polymer composition of the present invention can be efficiently produced by using at least one of the above-mentioned specific hydrocarbon-based surfactants. Furthermore, the TFE-based polymer composition of the present invention can be produced using two or more of the above-mentioned specific hydrocarbon-based surfactants simultaneously, or can be produced using other compounds having surface-active properties other than the above-mentioned specific hydrocarbon-based surfactants simultaneously, as long as the compounds are volatile or can remain in a molded article composed of the TFE-based polymer.

[0668] As the other compounds having surface active properties, for example, those described in JP-A-2013-542308, JP-A-2013-542309, and JP-A-2013-542310 can be used.

[0669] Other compounds having surface active properties may be surfactants having a hydrophilic portion and a hydrophobic portion on the same molecule, such as hydrocarbon surfactants (excluding the above-mentioned specific hydrocarbon surfactants). These may be cationic, nonionic or anionic.

[0670] In the above compound, the ratio of hydrogen atoms bonded to carbon atoms to be substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0671] Cationic surfactants generally have a positively charged hydrophilic portion such as an alkylated ammonium halide such as an alkylated ammonium bromide and a hydrophobic portion such as a long-chain fatty acid.

[0672] The cationic surfactant preferably has a ratio of fluorine atoms replacing hydrogen atoms bonded to carbon atoms of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0673] Anionic surfactants generally have a hydrophilic portion such as a carboxylate, sulfonate, or sulfate and a hydrophobic portion such as an alkyl group as a long-chain hydrocarbon portion.

[0674] In the anionic surfactant, the ratio of fluorine atoms replacing hydrogen atoms bonded to carbon atoms is preferably 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0675] Nonionic surfactants generally do not contain charged groups and have a hydrophobic portion that is a long-chain hydrocarbon. The hydrophilic portion of a nonionic surfactant contains a water-soluble functional group such as a vinyl ether chain derived from polymerization with ethylene oxide.

[0676] The nonionic surfactant preferably has a ratio of fluorine atoms replacing hydrogen atoms bonded to carbon atoms of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0677] Examples of nonionic surfactants

[0678] Polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, glyceride, and derivatives thereof.

[0679] Specific examples of the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like.

[0680] Specific examples of polyoxyethylene alkylphenyl ether include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0681] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, and the like.

[0682] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0683] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0684] Specific examples of glycerides include glyceryl monotetradecanoate, glyceryl monostearate, glyceryl monooleate, and the like.

[0685] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, and polyoxyethylene alkyl ether phosphates.

[0686] The above-mentioned ethers and esters may have an HLB value of 10-18.

[0687] Examples of the nonionic surfactant include Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), and Tergitol (registered trademark) L series manufactured by Dow Chemical Company; Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m to 22, n to 23)) and Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10) manufactured by BASF.

[0688] Examples of the anionic hydrocarbon surfactant include Versatic (registered trademark) 10 manufactured by Resolution Performance Products and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0689] As other compounds having surface activity, there can be mentioned RLM (wherein, R is a linear or branched alkyl group with or without a substituent having 1 or more carbon atoms, or a cyclic alkyl group with or without a substituent having 3 or more carbon atoms, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. L is -ArSO3 -、 -SO3 -、 -SO4-, -PO3 - or -COO - , M is H, metal atom, NR 5 4(R 5 They may be the same or different and are H or an organic group (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. -ArSO3 - is an anionic surfactant represented by aryl sulfonate. 5 It is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms.

[0690] Specifically, lauric acid represented by CH3-(CH2) n-LM (wherein n is an integer of 6 to 17. L and M are the same as above).

[0691] A mixture of substances in which R is an alkyl group having 12 to 16 carbon atoms and LM is sulfate or sodium dodecyl sulfate (SDS) can also be used.

[0692] Other compounds having surface activity include R 6 (-LM)2(where R 6 It is a linear or branched alkylene group with or without a substituent having 1 or more carbon atoms, or a cyclic alkylene group with or without a substituent having 3 or more carbon atoms. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. L is -ArSO3 -、 -SO3 -、 -SO4-, -PO3 - or -COO - , M is H, metal atom, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5 is H or an organic group (preferably an organic group without fluorine), -ArSO3 - It is an anionic surfactant shown by aryl sulfonate.

[0693] Other compounds having surface activity include R 7 (-LM)3(where R 7 It is a linear or branched alkynyl group with 1 or more carbon atoms, which may be substituted, or a cyclic alkynyl group with 3 or more carbon atoms, which may be substituted. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. L is -ArSO3 -、 -SO3 -、 -SO4-, -PO3 - or -COO - , M is H, metal atom, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5 Is H or an organic group (preferably an organic group without fluorine). -ArSO3 - It is an anionic surfactant shown by aryl sulfonate.

[0694] Examples of siloxane hydrocarbon surfactants include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of siloxane surfactants consists of a distinct hydrophobic portion and a hydrophilic portion. The hydrophobic portion comprises one or more dihydrocarbylsiloxane units, where all the substituents on the silicon atoms are hydrocarbons.

[0695] When the carbon atoms 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 substituents on the carbon atoms of the hydrocarbon group are hydrogen.

[0696] The siloxane surfactant preferably has a ratio of fluorine atoms replacing hydrogen atoms bonded to carbon atoms of 50% or less, more preferably 25% or less, further preferably 10% or less, and most preferably 0% (completely unsubstituted with fluorine atoms).

[0697] The hydrophilic portion of a silicone surfactant may contain one or more polar moieties, including ionic groups such as sulfate, sulfonate, phosphonate, phosphate, carboxylate, carbonate, sulfosuccinate, taurate (as a free acid, salt, or ester), phosphine oxide, betaine, betaine copolyol, and quaternary ammonium salts. The ionic hydrophobic portion may also contain an ionically functionalized silicone grafted portion.

[0698] Examples of such silicone hydrocarbon surfactants include polydimethylsiloxane-grafted (meth)acrylates, polydimethylsiloxane-grafted polyacrylates, and polydimethylsiloxane-grafted quaternary amines.

[0699] The polar portion of the hydrophilic portion of a silicone surfactant can include nonionic groups formed from polyethers such as polyethylene oxide (PEO) and mixed polyethylene oxide / propylene oxide polyethers (PEO / PPO); monosaccharides and disaccharides; and water-soluble heterocycles such as pyrrolidone. The ratio of ethylene oxide to propylene oxide (EO / PO) can vary in mixed polyethylene oxide / propylene oxide polyethers.

[0700] The hydrophilic portion of the silicone surfactant may also comprise a combination of an ionic portion and a nonionic portion. Examples of such portions include ionic end-functionalized or randomly functionalized polyethers or polyols. Preferred in the practice of the present invention are silicones having a nonionic portion, i.e., nonionic silicone surfactants.

[0701] The hydrophobic and hydrophilic portions of the structure of a siloxane surfactant can be arranged in the form of a diblock polymer (AB), a triblock polymer (ABA) (where "B" represents the siloxane portion of the molecule), or a multiblock polymer. Alternatively, the siloxane surfactant can include a graft polymer.

[0702] Silicone hydrocarbon surfactants are also disclosed in US Pat. No. 6,841,616.

[0703] Examples of the siloxane-based anionic hydrocarbon surfactant include Noveon (registered trademark) manufactured by Lubrizol Advanced Materials, Inc., and SilSense available from Consumer Specialties. TM PE-100 silicone, SilSense TM CA-1 silicone, etc.

[0704] Examples of the anionic hydrocarbon surfactant include sulfosuccinate surfactant Lankropol (registered trademark) K8300 manufactured by Akzo Nobel Surface Chemistry LLC.

[0705] Examples of the sulfosuccinate surfactant include diisodecyl sulfosuccinate sodium salt (Emulsogen (registered trademark) SB10 manufactured by Clariant), diisotridecyl sulfosuccinate sodium salt (Polirol (registered trademark) TR / LNA manufactured by Cesapinia Chemicals), and the like.

[0706] Other examples of compounds having surface active properties include PolyFox (registered trademark) surfactants manufactured by Omnova Solutions, Inc. TM PF-156A, PolyFox TM PF-136A, etc.).

[0707] As other compounds having surface active properties, anionic hydrocarbon surfactants are preferred. As anionic hydrocarbon surfactants, the above-mentioned ones can be used, and for example, the following hydrocarbon surfactants can also be preferably used.

[0708] Examples of the anionic hydrocarbon surfactant include the following formula (α):

[0709] R 100 -COOM (α)

[0710] (Where R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 101 R is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. 101 The organic group of R is preferably an alkyl group. 101 It is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms.

[0711] From the perspective of surface activity, R 100 The number of carbon atoms in is preferably 2 or more, more preferably 3 or more. In addition, from the perspective of water solubility, R 100 The number of carbon atoms is preferably 29 or less, more preferably 23 or less.

[0712] Examples of the metal atom of M include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. M is preferably H, a metal atom, or NR 101 4. More preferably, H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 101 4. H, Na, K, Li or NH4 is further preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0713] Examples of the compound (α) include R 102 -COOM (where R 102 It is a linear or branched alkyl, alkenyl, alkylene or alkenylene group with or without a substituent having 1 or more carbon atoms, or a cyclic alkyl, alkenyl, alkylene or alkenylene group with or without a substituent having 3 or more carbon atoms, which may contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. M is the same as above. An anionic surfactant represented by ).

[0714] Specifically, CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28 and M is the same as above).

[0715] From the viewpoint of emulsion stability, the compound (α) may not contain a carbonyl group (except for the carbonyl group in the carboxyl group).

[0716] Preferred examples of the hydrocarbon-containing surfactant not containing a carbonyl group include the following formula (A1):

[0717] R 103 -COO-M (A1)

[0718] (Where R 103 is an alkyl, alkenyl, alkylene or alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond. M is H, a metal atom, NR 101 4. An imidazolium which may have a substituent group, a pyridinium which may have a substituent group, or a phosphonium which may have a substituent group. 101 are the same or different and are H or an organic group (preferably an organic group not containing fluorine). ) compound.

[0719] In the above formula (A1), R 103 Preferably, it is an alkyl group or an alkenyl group (which may contain an ether group). 103 The alkyl or alkenyl group in R may be linear or branched. 103 The number of carbon atoms in is not limited and is, for example, 2 to 29.

[0720] When the above alkyl group is linear, R 103 The number of carbon atoms in is preferably 3 to 29, more preferably 5 to 23. When the above alkyl group is branched, R 103 The number of carbon atoms in the alkyl group is preferably 5-35, more preferably 11-23.

[0721] When the alkenyl group is 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 in the alkyl group is preferably 2-29, more preferably 9-23.

[0722] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a tert-butyl group, and a vinyl group.

[0723] Examples of the compound (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, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)-linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, palmitoleic acid, cis-1- ... 6-hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, octadecatetraenoic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, primapentaenoic acid, eicosapentaenoic acid, docosapentaenoic acid, eugenol acid, tetracospentaenoic acid, docosahexaenoic acid, herring acid, and salts thereof.

[0724] In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof is preferred.

[0725] Examples of the salt include a salt in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 11 4. An imidazolium which may have a substituent group, a pyridinium which may have a substituent group, or a phosphonium which may have a substituent group, without particular limitation.

[0726] In addition, examples of the anionic hydrocarbon surfactant include the following formula (β):

[0727] R 100 -SO3M(β)

[0728] (Where R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 101 R is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. 101 The organic group of R is preferably an alkyl group. 101 It is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms.

[0729] From the perspective of surface activity, R 100The number of carbon atoms in is preferably 2 or more, more preferably 3 or more. In addition, from the perspective of water solubility, R 100 The number of carbon atoms is preferably 29 or less, more preferably 23 or less.

[0730] Examples of the metal atom of M include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. M is preferably H, a metal atom, or NR 101 4. More preferably, H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 101 4. H, Na, K, Li or NH4 is further preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0731] Examples of the compound (β) include R 102 -SO3M(where R 102 It is a linear or branched alkyl, alkenyl, alkylene or alkenylene group with or without a substituent having 1 or more carbon atoms, or a cyclic alkyl, alkenyl, alkylene or alkenylene group with or without a substituent having 3 or more carbon atoms, which may contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. M is the same as above. An anionic surfactant represented by ).

[0732] Specifically, CH3-(CH2) n -SO3M (wherein n is an integer of 2 to 28. M is the same as above).

[0733] From the viewpoint of emulsion stability, the compound (β) may not contain a carbonyl group (except for the carbonyl group in the carboxyl group).

[0734] Preferred examples of the hydrocarbon-containing surfactant not containing a carbonyl group include the following formula (B1):

[0735] R 103 -SO3-M(B1)

[0736] (Where R 103 is an alkyl, alkenyl, alkylene or alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond. M is H, a metal atom, NR 101 4. An imidazolium which may have a substituent group, a pyridinium which may have a substituent group, or a phosphonium which may have a substituent group. 101 are the same or different and are H or an organic group (preferably an organic group not containing fluorine). ) compound.

[0737] In the above formula (B1), R 103Preferably, it is an alkyl group or an alkenyl group (which may contain an ether group). 103 The alkyl or alkenyl group in R may be linear or branched. 103 The number of carbon atoms in is not limited and is, for example, 2 to 29.

[0738] When the above alkyl group is linear, R 103 The number of carbon atoms in is preferably 3 to 29, more preferably 5 to 23. When the above alkyl group is branched, R 103 The number of carbon atoms in the alkyl group is preferably 5-35, more preferably 11-23.

[0739] When the alkenyl group is 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 in the alkyl group is preferably 2-29, more preferably 9-23.

[0740] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a tert-butyl group, and a vinyl group.

[0741] Examples of the compound (β) include aliphatic, unsaturated aliphatic, aromatic, and other sulfonic acids, aliphatic, unsaturated aliphatic, aromatic, and other sulfates, and salts thereof.

[0742] Examples of the sulfonic acid include 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, perfluorobutanesulfonic acid, linear alkylbenzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, DBS, naphthalenesulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, and butylnaphthalenesulfonic acid. Examples of the sulfuric acid ester include sodium alkyl sulfate, α-sulfo fatty acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, α-olefin sulfonates, lauryl sulfuric acid, myristyl sulfuric acid, lauryl alcohol polyether sulfate, and polyoxyethylene alkylphenolsulfonic acid.

[0743] As the above-mentioned compound (β), at least one selected from the group consisting of saturated aliphatic and aromatic sulfates, and salts thereof is particularly preferred, and at least one selected from the group consisting of sodium alkyl sulfate, α-sulfo fatty acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, α-olefin sulfonates, lauryl sulfuric acid, myristyl sulfuric acid, lauryl alcohol polyether sulfate, polyoxyethylene alkylphenol sulfonic acid, and salts thereof is more preferred.

[0744] Examples of the salt include a salt in which the hydrogen of the sulfonic acid group is a metal atom of the above formula M, NR 11 4. An imidazolium which may have a substituent group, a pyridinium which may have a substituent group, or a phosphonium which may have a substituent group, without particular limitation.

[0745] Examples of the anionic hydrocarbon surfactant include the following formula (1-0A):

[0746] [Chemistry 31]

[0747]

[0748] (Where R 1A ~R 5A is H, a monovalent hydrocarbon group which may contain an ester group between carbon atoms, or a general formula: -X A -A represented by the group. 2A and R 5A At least one of them represents the general formula: -X A -The group represented by A.

[0749] X A The same or different in each occurrence, is a divalent hydrocarbon group or a bond;

[0750] A is the same or different in each occurrence and is -COOM (M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group (preferably an organic group not containing fluorine);

[0751] R 1A ~R 5A Any two of them can be bonded to each other to form a ring. ) shown in the surfactant (1-0A) and the like.

[0752] In the general formula (1-0A), R 1A ~R 5A The number of carbon atoms in the monovalent hydrocarbon group which 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 may be bonded to each other to form a ring. As the monovalent hydrocarbon group which may contain an ester group between carbon atoms, an alkyl group is preferable.

[0753] Where, X A The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 50, more preferably 5 to 20. Examples of the divalent hydrocarbon group include an alkylene group and an alkanediyl group, and an alkylene group is preferred.

[0754] In the general formula (1-0A), R 2A and R 5A Any one of them is preferably the above general formula: -X A -A, R 2AMore preferably, it is the above general formula: -X A -The group represented by A.

[0755] In the general formula (1-0A), as a suitable embodiment, R 2A The general formula is: -X A -A represented by the group, R 1A 、R 3A 、R 4A and R 5A In this case, X A It is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0756] In the general formula (1-0A), as a suitable embodiment, R 2A The general formula is: -X A -A represented by the group, R 1A and R 3A -Y A -R 6 The group shown, Y A are the same or different in each occurrence and are -COO-, -OCO- or a bond, R 6 In each occurrence, the alkyl group may be the same or different and may have 2 or more carbon atoms. In this case, R 4A and R 5A For H.

[0757] Examples of the hydrocarbon surfactant represented by the general formula (1-0A) include glutaric acid or its salts, adipic acid or its salts, pimelic acid or its salts, suberic acid or its salts, azelaic acid or its salts, and sebacic acid or its salts.

[0758] In addition, the aliphatic carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) can be a 2-chain 2-hydrophilic group type synthetic surfactant. For example, as a gemini surfactant, there can be cited Geminisurf (Chukyo Oil Co., Ltd.), Gemsurf α142 (lauryl with 12 carbon atoms), Gemsurf α102 (10 carbon atoms), Gemsurf α182 (14 carbon atoms), etc.

[0759] Examples of the anionic hydrocarbon surfactant include the following formula I:

[0760] R-(XZ) n (I)

[0761] (wherein R is a hydrophobic hydrocarbon portion comprising 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 portion does not contain a siloxane unit. Each X may be the same or different and represents an ionic hydrophilic portion. Each Z may be the same or different and represents one or more counter ions of the ionic hydrophilic portion. n is 1 to 3.) Compound I shown.

[0762] Compound I exhibits low reactivity with polymerization initiators and / or growing fluoropolymer radicals in the emulsion polymerization of fluoromonomers.

[0763] Compound I preferably comprises the formula:

[0764] [Chemistry 32]

[0765]

[0766] (Where Y + is hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal or alkaline earth metal. ) is the substituted portion.

[0767] Compound I is preferably represented by the following formula II:

[0768] [Chemistry 33]

[0769]

[0770] (Where R 2’ and R 2”’ are the same or different, and are saturated or unsaturated, acyclic or cyclic aliphatic groups having 4 to 16 carbon atoms, R 2’ and R 2”’ The total percentage of CH3 groups in the group relative to the total percentage of CH3, CH2 and CH groups is at least about 70%, or R 2’ and R 2”’ The alkyl groups are bonded to each other to form a saturated or unsaturated aliphatic ring which may contain ether or ester bonds, wherein 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 Y is hydrogen, methoxy, ethoxy or phenoxy. + is hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal or alkaline earth metal. ) is compound II shown.

[0771] As compound II, for example, the following compounds are preferred.

[0772] [Chemistry 34]

[0773]

[0774] In the above formula, Y + It may be hydrogen, ammonium, or an alkali metal.

[0775] Compound I is also preferably of the following formula III:

[0776] [Chemistry 35]

[0777]

[0778] (Where R 3 、R 4’ and R 4” are the same or different and are hydrogen or a saturated or unsaturated, acyclic or cyclic aliphatic group having 4 to 16 carbon atoms, R 3 、R 4’ and R 4” The total percentage of CH3 in the group relative to the total percentage of CH3, CH2 and CH groups is at least about 70%. 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. + is hydrogen, ammonium, quaternary ammonium, nitrogen heterocycle, alkali metal or alkaline earth metal. ) is compound III shown.

[0779] As compound III, for example, the following compounds are preferred.

[0780] [Chemistry 36]

[0781]

[0782] In the above formula, Y + It may be hydrogen, ammonium, or an alkali metal.

[0783] In the production method of the present invention, two or more hydrocarbon-based surfactants may be used simultaneously.

[0784] The TFE-based polymer composition of the present invention can be obtained by a production method comprising the following polymerization step: in the presence of a hydrocarbon-based surfactant and a polymerization initiator, tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene are polymerized in an aqueous medium having a pH of 4.0 or higher to obtain a TFE-based polymer.

[0785] Conventionally, the polymerization process for producing TFE-based polymers uses an acidic polymerization initiator, resulting in the pH of the aqueous medium used for polymerization being less than 4.0. The present inventors conducted intensive research and unexpectedly discovered that by using an aqueous medium with a pH of 4.0 or higher for polymerization, polymerization stability is improved, allowing the production of high-molecular-weight TFE-based polymers.

[0786] In the above production method, tetrafluoroethylene alone, or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene, are polymerized in an aqueous medium having a pH of 4.0 or higher. The pH may be 4.0 or higher, preferably greater than 4.0, more preferably 4.5 or higher, even more preferably 5.0 or higher, still more preferably 5.5 or higher, even more preferably 6.0 or higher, particularly preferably 6.5 or higher, particularly preferably 7.0 or higher, particularly preferably 7.5 or higher, and particularly preferably 8.0 or higher. The upper limit of the pH is not particularly limited and may be, for example, 13.0 or lower. From the perspective of corrosion of the polymerization vessel, the pH is preferably 12.0 or lower, more preferably 11.5 or lower, and even more preferably 11.0 or lower.

[0787] The above pH can be measured with a pH meter.

[0788] In the above production method, the method for adjusting the pH of the aqueous medium to 4.0 or higher is not particularly limited. For example, the pH can be adjusted to 4.0 or higher by using an alkaline aqueous solution, an alkaline aqueous dispersion, or a pH adjuster.

[0789] In addition, even when using a polymerization initiator that exhibits acidity when dissolved in an aqueous medium, the pH can be adjusted to 4.0 or above by adding an alkaline compound such as sodium hydroxide. - The compound may be a compound such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides; ammonia; amines, etc., without particular limitation. The polymerization step may include a step of adding an alkali compound to the aqueous medium.

[0790] In the above production method, the pH of the aqueous medium may be 4.0 or higher throughout the entire polymerization process. Alternatively, the pH may be 4.0 or higher during the middle phase of the polymerization process, or the pH may be 4.0 or higher during the second half of the polymerization process. Alternatively, the pH may be 4.0 or higher during both the middle and second half of the polymerization process.

[0791] For example, in the polymerization step, the pH of the aqueous medium is preferably 4.0 or higher when the polymer solids concentration is 3% by mass or higher. In other words, the production method preferably includes a polymerization step of polymerizing tetrafluoroethylene alone, or tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene, in an aqueous medium in the presence of a hydrocarbon surfactant and a polymerization initiator to obtain a TFE-based polymer, and the pH of the aqueous medium is preferably 4.0 or higher when the polymer solids concentration is 3% by mass or higher. The aqueous medium more preferably has a pH of 4.0 or higher when the polymer solids concentration is 5% by mass or higher, further preferably has a pH of 4.0 or higher when the polymer solids concentration is 8% by mass or higher, even more preferably has a pH of 4.0 or higher when the polymer solids concentration is 10% by mass or higher, even more preferably has a pH of 4.0 or higher when the polymer solids concentration is 15% by mass or higher, particularly preferably has a pH of 4.0 or higher when the polymer solids concentration is 18% by mass or higher, more preferably has a pH of 4.0 or higher when the polymer solids concentration is 20% by mass or higher, and even more preferably has a pH of 4.0 or higher when the polymer solids concentration is 25% by mass or higher.

[0792] In the polymerization step, the pH of the aqueous medium is preferably maintained at 4.0 or higher from the time the polymer solids concentration reaches 25% by mass until the end of polymerization, more preferably at 4.0 or higher from the time the polymer solids concentration reaches 20% by mass until the end of polymerization, further preferably at 4.0 or higher from the time the polymer solids concentration reaches 18% by mass until the end of polymerization, still more preferably at 4.0 or higher from the time the polymer solids concentration reaches 15% by mass until the end of polymerization, particularly preferably at 4.0 or higher from the time the polymer solids concentration reaches 10% by mass until the end of polymerization, particularly preferably at 4.0 or higher from the time the polymer solids concentration reaches 8% by mass until the end of polymerization, more preferably at 4.0 or higher from the time the polymer solids concentration reaches 5% by mass until the end of polymerization, and further preferably at 4.0 or higher from the time the polymer solids concentration reaches 3% by mass until the end of polymerization.

[0793] In the polymerization step, the pH of the aqueous medium is preferably 4.0 or higher when the polymer solids concentration is less than 15% by mass. More preferably, the pH of the aqueous medium is 4.0 or higher when the polymer solids concentration is 3% by mass or higher and less than 15% by mass. Even more preferably, the pH of the aqueous medium is 4.0 or higher when the polymer solids concentration is 5% by mass or higher and less than 15% by mass. Even more preferably, the pH of the aqueous medium is 4.0 or higher when the polymer solids concentration is 8% by mass or higher and less than 15% by mass. Even more preferably, the pH of the aqueous medium is 4.0 or higher when the polymer solids concentration is 10% by mass or higher and less than 15% by mass.

[0794] In addition, in the above-mentioned polymerization process, the pH of the aqueous medium is preferably maintained at above 4.0 during the period when the polymer solid content concentration is from 10 mass % to 15 mass %, more preferably the pH of the aqueous medium is maintained at above 4.0 during the period when the polymer solid content concentration is from 8 mass % to 15 mass %, and further preferably the pH of the aqueous medium is maintained at above 4.0 during the period when the polymer solid content concentration is from 5 mass % to 15 mass %.

[0795] In any case, the pH of the aqueous medium is 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, particularly preferably 6.5 or higher, more preferably 7.0 or higher, more preferably 7.5 or higher, and even more preferably 8.0 or higher.

[0796] In the above-mentioned polymerization step, the pH of the aqueous medium is preferably 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, particularly more preferably 99% or more, and particularly preferably 100%) of the period from the start of polymerization to the time when the polymer solid content concentration reaches 3 mass% (preferably 5 mass%, more preferably 8 mass%, further preferably 10 mass%, even more preferably 15 mass%, particularly more preferably 18 mass%, particularly more preferably 20 mass%, and particularly preferably 25 mass%).

[0797] In the above-mentioned polymerization step, the pH of the aqueous medium is preferably 4.0 or higher for 60% (preferably 70% or higher, more preferably 80% or higher, more preferably 90% or higher, even more preferably 95% or higher, particularly preferably 99% or higher, and particularly preferably 100%) of the period from the point in time when the polymer solid content 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 point in time when the polymer solid content concentration is 15% by mass.

[0798] In the above-mentioned polymerization process, the pH of the aqueous medium is preferably 4.0 or above during 60% (preferably 70% or above, more preferably 80% or above, further preferably 90% or above, even more preferably 95% or above, especially more preferably 99% or above, and particularly preferably 100%) of the period from the point when the polymer solid content concentration is 15% by mass to the point when the polymer solid content concentration is 18% by mass (preferably 20% by mass, more preferably 25% by mass).

[0799] In the above-mentioned polymerization step, the pH of the aqueous medium is preferably 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, more preferably 99% or more, and particularly preferably 100%) of the period from the time when the polymer solid content concentration is 25% by mass (preferably 20% by mass, more preferably 18% by mass, further preferably 15% by mass, still more preferably 10% by mass, particularly more preferably 8% by mass, particularly preferably 5% by mass, more preferably 3% by mass, and further preferably the start of polymerization) to the time of termination of polymerization.

[0800] In any case, the pH of the aqueous medium is 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, particularly preferably 6.5 or higher, more preferably 7.0 or higher, more preferably 7.5 or higher, and even more preferably 8.0 or higher.

[0801] In the above production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid hydrocarbon surfactant are not particularly limited, and for example, the compound (α) exemplified in the above-mentioned other compounds having surface activity can be suitably used.

[0802] In the above production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and also preferably a sulfonic acid hydrocarbon surfactant. The anionic hydrocarbon surfactant and the sulfonic acid hydrocarbon surfactant are not particularly limited. For example, the compound (β) exemplified in the above-mentioned other compounds having surface activity can be suitably used.

[0803] Even without using the aforementioned specific hydrocarbon-based surfactant, the TFE-based polymer composition of the present invention can be obtained by a process comprising a polymerization step of polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon-based surfactant and a polymerization initiator to obtain a TFE-based polymer, wherein the hydrocarbon-based surfactant includes a salt of the hydrocarbon-based surfactant. In other words, at least a portion of the anionic hydrocarbon-based surfactant in the polymerization step is in the form of a salt.

[0804] The present inventors have conducted intensive studies and unexpectedly found that when the anionic hydrocarbon surfactant includes a salt of the anionic hydrocarbon surfactant, the polymerization stability is improved and a TFE polymer having a large molecular weight can be produced.

[0805] This is considered to be because the inclusion of the salt increases the water solubility of the anionic surfactant, making it easier for the emulsifying property to be exhibited.

[0806] The above-mentioned anionic hydrocarbon-based surfactant will be described later.

[0807] Whether the anionic hydrocarbon-based surfactant contains a salt of the hydrocarbon-based surfactant can be confirmed by measuring the electrical conductivity.

[0808] In the above-mentioned production method, the concentration of the salt of the anionic hydrocarbon-based surfactant in the above-mentioned anionic hydrocarbon-based surfactant is preferably 50 mass%, more preferably 60 mass% or more, further preferably 70 mass% or more, even more preferably 80 mass% or more, particularly preferably 90 mass% or more, and particularly preferably 95 mass% or more, relative to the total mass of the anionic hydrocarbon-based surfactant.

[0809] The ratio of the above salts can be determined by solution concentration and conductivity.

[0810] In the above production method, the hydrocarbon-based surfactant is more preferably a carboxylic acid-type hydrocarbon-based surfactant. The hydrocarbon-based surfactant does not contain fluorine.

[0811] In the salt of anionic hydrocarbon surfactant, the cation (excluding hydrogen atom) that replaces the hydrogen atom of the acid is, for example, a metal atom, NR y 4(R y They may be the same or different and are H or an organic group (preferably an organic group not containing fluorine), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. y It is preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms.

[0812] As the cation in the salt of the anionic hydrocarbon surfactant, a metal atom or NR y 4. NR is more preferred y 4. NH4 is further preferred.

[0813] Since conductivity is greatly affected by temperature and changes, the conductivity was measured by maintaining the sample solution temperature at 25° C. using a thermostatic bath and the glass tube (cell) of the pH meter at the same temperature.

[0814] In the above production method, the polymerization step is preferably carried out substantially in the absence of the hydrocarbon-based surfactant in the form of an organic acid. By carrying out the polymerization substantially in the absence of the hydrocarbon-based surfactant in the form of an organic acid, polymerization stability is further improved, and a high molecular weight TFE-based polymer can be obtained.

[0815] Substantially in the absence of the hydrocarbon surfactant in the form of an organic acid means that the concentration of the organic acid is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, particularly preferably 0.05 mass% or less, and particularly preferably 0.01 mass% or less, relative to the mass of the obtained aqueous dispersion.

[0816] In this specification, "organic acid" refers to an organic compound showing acidity. Examples of organic acids include carboxylic acids having a -COOH group and sulfonic acids having a -SO3H group. Carboxylic acids are preferred because they can easily adjust the pH of an aqueous solution containing the organic acid.

[0817] Furthermore, the "form of an organic acid" refers to a form in which H of an acidic group (eg, a -COOH group, a -SO 3 H group, etc.) contained in the organic acid is not free.

[0818] In the above production method, the hydrocarbon-based surfactant is an anionic hydrocarbon-based surfactant.

[0819] In the polymerization step described above, the amount of the hydrocarbon surfactant at the start of polymerization is preferably greater than 50 ppm relative to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or greater, more preferably 70 ppm or greater, even more preferably 80 ppm or greater, and even more preferably 100 ppm or greater. The upper limit is not particularly limited, but is preferably 10,000 ppm, more preferably 5,000 ppm. By setting the amount of the hydrocarbon surfactant at the start of polymerization within the above range, the average primary particle size is smaller, and an aqueous dispersion with greater stability can be obtained.

[0820] It should be noted that polymerization can be said to begin when the gaseous TFE in the reactor is converted into a TFE-based polymer and a pressure drop occurs in the reactor. U.S. Patent No. 3,391,099 (Punderson) discloses the dispersion polymerization of tetrafluoroethylene in an aqueous medium, which consists of two independent stages of the polymerization process: the formation of a polymer core as a nucleation site, and then a growth stage including the polymerization of established particles. It should be noted that polymerization generally begins when both the monomer to be polymerized and the polymerization initiator are filled into the reactor. In addition, in the present invention, the additive involved in the formation of the nucleation site is a nucleating agent.

[0821] The polymerization step preferably includes an addition step of adding a composition containing a hydrocarbon-based surfactant after the start of polymerization. This addition step further improves the stability of the polymerization and allows a TFE-based polymer with a higher molecular weight to be obtained.

[0822] The hydrocarbon-based surfactant may be in the form of a solid (eg, a powder of the hydrocarbon-based surfactant) or a liquid.

[0823] The composition may contain only a hydrocarbon surfactant, or may be a solution or dispersion of the hydrocarbon surfactant comprising a hydrocarbon surfactant and a liquid medium. Therefore, the addition step may be considered a step of adding the hydrocarbon surfactant monomer or the composition comprising the hydrocarbon surfactant after the start of polymerization.

[0824] The hydrocarbon-based surfactant is not limited to one type, and may be a mixture of two or more types.

[0825] The liquid medium may be either an aqueous medium or an organic solvent, or a combination of an aqueous medium and an organic solvent may be used.

[0826] Specific examples of the composition include an aqueous solution in which a hydrocarbon-based surfactant is dissolved in an aqueous medium, and an aqueous dispersion in which a hydrocarbon-based surfactant is dispersed in an aqueous medium.

[0827] The hydrocarbon surfactant added in the above-mentioned addition step is preferably present in an amount of 0.0001 to 10% by mass relative to the aqueous medium. It is more preferably present in an amount of 0.001% by mass or greater, further preferably present in an amount of 0.01% by mass or greater, and particularly preferably present in an amount of 0.05% by mass or greater relative to the aqueous medium. Furthermore, it is more preferably present in an amount of 5% by mass or less, further preferably present in an amount of 3% by mass or less, and particularly preferably present in an amount of 1% by mass or less relative to the aqueous medium.

[0828] From the viewpoint of improving polymerization stability and obtaining a TFE-based polymer having a higher molecular weight, the composition is preferably an aqueous solution containing a hydrocarbon-based surfactant and having a pH of 5.0 or higher.

[0829] The pH of the aqueous solution is more preferably 6.0 or higher, further preferably 6.5 or higher, still more preferably 7.0 or higher, particularly preferably 7.5 or higher, and particularly preferably 8.0 or higher. The upper limit of the pH is not particularly limited and may be 12.0 or lower, or 11.0 or lower.

[0830] The hydrocarbon-based surfactant in the above-mentioned adding step is preferably an anionic hydrocarbon-based surfactant, more preferably a carboxylic acid-based hydrocarbon-based surfactant.

[0831] The anionic hydrocarbon surfactant and the carboxylic acid hydrocarbon surfactant are not particularly limited, and for example, the compound (α) exemplified in the above-mentioned other compounds having surface active properties can be suitably used.

[0832] As the carboxylic acid type hydrocarbon surfactant used in the polymerization step and the addition step, it is preferable to select from the above-mentioned surfactant (e), the above-mentioned formula: 6 (-LM)2 represented by anionic surfactant, and the above formula: R 7 At least one selected from the group consisting of anionic surfactants represented by (-LM)3 having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.), the aforementioned compound (α), the aforementioned surfactant (1-0A), and surfactants obtained by subjecting these surfactants to free radical treatment or oxidation treatment. The aforementioned carboxylic acid-type hydrocarbon surfactant may be used alone or as a mixture of two or more.

[0833] The above compound (α) includes not only the above formula: R 102 -COOM (where R 102 and M are the same as above. ) represented by anionic hydrocarbon surfactants (preferably compounds represented by formula (A1)), also include anionic surfactants represented by the above formula: RLM (wherein R, L and M are the same as above), substances having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted by an inorganic cation (such as a metal atom, ammonium, etc.) in the above surfactants (c) and (d), etc.

[0834] The carboxylic acid type hydrocarbon surfactant is preferably the compound (α), more preferably selected from the compound represented by the formula (A1), the compound represented by the formula (c), c COOX c The compound of the above formula (d) d COOX d The compound of the above formula (e) e For-COOM e The present invention is preferably selected from at least one of the group consisting of a compound represented by the above formula (A1) and a surfactant after the compound is subjected to a free radical treatment or an oxidation treatment, a compound wherein A is -COOM in the above formula (1-0A), and at least one of the group consisting of a surfactant after the compound is subjected to a free radical treatment or an oxidation treatment.

[0835] In particular, at least one selected from the group consisting of lauric acid, capric acid, tetradecanoic acid, pentadecanoic acid, palmitic acid and their salts, and compounds obtained by subjecting these compounds to free radical treatment or oxidation treatment is preferred. Examples of the above-mentioned salt include a metal atom of the above-mentioned formula M in which the hydrogen of the carboxyl group is present, NR 101 4. The substance may be substituted imidazolium, may be substituted pyridinium, or may be substituted phosphonium, but is not particularly limited.

[0836] In the above-mentioned production method, tetrafluoroethylene is preferably polymerized in the substantial absence of a fluorinated surfactant.

[0837] In the above-mentioned production method, "substantially in the absence of a fluorinated surfactant" means that the fluorinated surfactant is present in an amount of 10 ppm by mass or less, preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, further preferably 10 ppb by mass or less, still more preferably less than 10 ppb by mass, still more preferably 1 ppb by mass or less, and particularly preferably less than 1 ppb by mass, relative to the aqueous medium.

[0838] Furthermore, “substantially in the absence of a fluorinated surfactant” also means that a fluorinated surfactant is not intentionally added.

[0839] Examples of the fluorinated surfactant include anionic fluorinated surfactants and the like.

[0840] The anionic fluorinated surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less in the portion excluding the anionic group.

[0841] Furthermore, the fluorine-containing surfactant may be a fluorine-containing surfactant having an anionic moiety with a molecular weight of 1000 or less, preferably 800 or less.

[0842] It should be noted that the above-mentioned "anionic part" refers to the part of the above-mentioned fluorinated surfactant other than the cation. For example, in the F(CF2) shown in the formula (I) described later n1 In the case of COOM, it is "F(CF2) n1 COO” part.

[0843] Examples of the fluorinated surfactant include those having a LogPOW of 3.5 or less. The LogPOW is the partition coefficient between 1-octanol and water and is represented by LogP [where P represents the ratio of the fluorinated surfactant concentration in octanol to the fluorinated surfactant concentration in water when a 1:1 octanol / water mixture containing the fluorinated surfactant undergoes phase separation].

[0844] The above LogPOW is calculated as follows: On column: TOSOH ODS-120T column ( HPLC was performed on standard substances with known octanol / water partition coefficients (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) under the following conditions: (a) a column temperature of 40°C, (b) a column temperature of 40°C, (c) a column temperature of 40°C, (d) a column temperature of 100°C, (e) a column temperature of 100°C, (f) a column temperature of 100°C, (g) a column temperature of 100°C, (h ...

[0845] Specific examples of the 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. 3,250,808. 3271341, 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.

[0846] Examples of the anionic fluorinated surfactant include the following general formula (N 0 ):

[0847] X n0 -Rf n0 -Y 0 (N 0 )

[0848] (Where X n0 For H, Cl or and F. Rf n0 It is a chain, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H groups are replaced by F. The alkylene group may contain one or more ether bonds, and some of the H groups may be replaced by Cl. 0is an anionic group).

[0849] Y 0 The anionic group may be -COOM, -SO2M or -SO3M, or may be -COOM or -SO3M.

[0850] M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is -H or an organic group.

[0851] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, and Li.

[0852] As R 7 , which can be H or C 1-10 The organic group can also be H or C 1-4 The organic group can also be H or C 1-4 of alkyl.

[0853] M can be H, metal atom or NR 7 4, can also be H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4, can also be H, Na, K, Li or NH4.

[0854] The above Rf n0 In the present invention, more than 50% of the H can be replaced by fluorine.

[0855] As the above general formula (N 0 ) can be exemplified by:

[0856] The following general formula (N 1 ):

[0857] X n0 -(CF2) m1 -Y 0 (N 1 )

[0858] (Where X n0 is H, Cl and F, m1 is an integer from 3 to 15, Y 0 The compound represented by the following general formula (N 2 ):

[0859] Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 )

[0860] (Where Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, X n1 F or CF3, Y 0 The compound represented by the following general formula (N 3 ):

[0861] Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 )

[0862] (Where Rf n2 is a partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y 0 The compound represented by the following general formula (N 4 ):

[0863] Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 )

[0864] (Where Rf n4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond, n1 and Y n2 The same or different, H or F, p is 0 or 1, Y 0 The compound represented by the above-defined substance); and the following general formula (N 5 ):

[0865] [Chemistry 37]

[0866]

[0867] (Where X n2 、X n3 and X n4 Rf may be the same or different and is H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond. n5 is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms and which may contain an ether bond, L is a connecting group, Y0 is the substance defined above. n2 、X n3 、X n4 and Rf n5 The total number of carbon atoms is 18 or less).

[0868] As the above general formula (N 0 ), more specifically, the compounds represented by the following general formula (I), perfluorocarboxylic acid (I) represented by the following general formula (II), perfluoropolyether carboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by the following general formula (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), perfluoroalkylalkylenesulfonic acid (VIII) represented by the following general formula (VIII), alkylalkylene carboxylic acid (IX) represented by the following general formula (IX), fluorocarboxylic acid (X) represented by the following general formula (X), alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI) and compound (XII) represented by the following general formula (XII).

[0869] The above-mentioned perfluorocarboxylic acid (I) is represented by the following general formula (I):

[0870] F(CF2) n1 COOM(I)

[0871] (where n1 is an integer from 3 to 14, M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group).

[0872] The above-mentioned ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II):

[0873] H(CF2) n2 COOM(II)

[0874] (wherein n2 is an integer of 4 to 15, and M is the substance defined above).

[0875] The above-mentioned perfluoropolyether carboxylic acid (III) is represented by the following general formula (III):

[0876] Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM(III)

[0877] (Where Rf1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is the substance defined above).

[0878] The above-mentioned perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV):

[0879] Rf 2 (CH2) n4 Rf 3 COOM(IV)

[0880] (Where Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is the substance defined above).

[0881] The above-mentioned alkoxy fluorocarboxylic acid (V) is represented by the following general formula (V):

[0882] Rf 4 -O-CY 1 Y 2 CF2-COOM(V)

[0883] (Where Rf 4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond, 1 and Y 2 are the same or different, are H or F, and M is the substance defined above).

[0884] The above-mentioned perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI):

[0885] F(CF2) n5 SO3M(VI)

[0886] (wherein n5 is an integer of 3 to 14, and M is the substance defined above).

[0887] The above-mentioned ω-H perfluorosulfonic acid (VII) is represented by the following general formula (VII):

[0888] H(CF2) n6 SO3M(VII)

[0889] (wherein n6 is an integer of 4 to 14, and M is the substance defined above).

[0890] The above-mentioned perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII):

[0891] Rf 5 (CH2) n7SO3M(VIII)

[0892] (Where Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is the substance defined above).

[0893] The above-mentioned alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX):

[0894] Rf 6 (CH2) n8 COOM(IX)

[0895] (Where Rf 6 is a linear or branched partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer of 1 to 3, and M is the substance defined above).

[0896] The above-mentioned fluorocarboxylic acid (X) is represented by the following general formula (X):

[0897] Rf 7 -O-Rf 8 -O-CF2-COOM(X)

[0898] (Where Rf 7 is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond, Rf 8 is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is defined as above).

[0899] The above-mentioned alkoxy fluorosulfonic acid (XI) is represented by the following general formula (XI):

[0900] Rf 9 -O-CY 1 Y 2 CF2-SO3M(XI)

[0901] (Where Rf 9 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain an ether bond and may contain chlorine, 1 and Y 2 are the same or different, are H or F, and M is the substance defined above).

[0902] The above compound (XII) is represented by the following general formula (XII):

[0903] [Chemistry 38]

[0904]

[0905] (Where X 1、X 2 and X 3 Rf may be the same or different and is H, F and a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond. 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a connecting group, Y 0 is an anionic group).

[0906] Y 0 It can be -COOM, -SO2M or -SO3M, or it can be -SO3M or COOM (wherein M is the substance defined above).

[0907] Examples of L include a single bond and a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms which may include an ether bond.

[0908] As described above, examples of the anionic fluorinated surfactant include carboxylic acid-based fluorinated surfactants and sulfonic acid-based fluorinated surfactants.

[0909] The TFE-based polymer composition of the present invention can be suitably produced by a production method comprising an addition step of adding at least one selected from the group consisting of a free radical scavenger and a decomposing agent for a polymerization initiator. The addition step is performed during the process of performing the above-mentioned emulsion polymerization in an aqueous medium. By adding a free radical scavenger or a decomposing agent for a 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 preferably used.

[0910] As the free radical scavenger, a compound that adds to the free radical in the polymerization system or does not have the ability to reinitiate after chain transfer is used. Specifically, a compound that has the following functions: easily undergoes chain transfer reaction with primary free radicals or propagating free radicals, and then generates stable free radicals that do not react with monomers, or easily reacts with

[0911] A primary free radical or a growing free radical undergoes an addition reaction to generate a stable free radical.

[0912] The activity of substances generally referred to as chain transfer agents is characterized by a chain transfer constant and a reinitiation efficiency. Among chain transfer agents, substances having a reinitiation efficiency of substantially 0% are referred to as free radical scavengers.

[0913] The radical scavenger can be, for example, a compound having a chain transfer constant with TFE at the polymerization temperature greater than the polymerization rate constant and having a substantially zero% reinitiation efficiency. "Substantially zero% reinitiation efficiency" means that the generated free radicals stabilize the radical scavenger.

[0914] Preferred are compounds having a chain transfer constant (Cs) with TFE at the polymerization temperature (=chain transfer rate constant (kc) / polymerization rate constant (kp)) greater than 0.1, and the chain transfer constant (Cs) of the above-mentioned compound is more preferably 0.5 or greater, further preferably 1.0 or greater, still more preferably 5.0 or greater, and particularly preferably 10 or greater.

[0915] The radical scavenger is preferably at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and copper chloride (CuCl 2 ).

[0916] Examples of the aromatic hydroxy compound include unsubstituted phenol, polyphenol, salicylic acid, m-salicylic acid, p-salicylic acid, gallic acid, and naphthol.

[0917] Examples of the unsubstituted phenol include o-nitrophenol, m-nitrophenol, p-nitrophenol, o-aminophenol, m-aminophenol, p-aminophenol, and p-nitrosophenol. Examples of the polyphenol include catechol, resorcinol, hydroquinone, pyrogallol, pyrogallol, and naphthol resorcinol.

[0918] Examples of the aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and benzidine.

[0919] Examples of the quinone compound include o-benzoquinone, m-benzoquinone, p-benzoquinone, 1,4-naphthoquinone, and alizarin.

[0920] Examples of the thiocyanate include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN).

[0921] Among these, the radical scavenger is preferably an aromatic hydroxy compound, more preferably unsubstituted phenol or polyphenol, and still more preferably hydroquinone.

[0922] From the perspective of reducing the standard specific gravity, the amount of the radical scavenger added is preferably an amount equivalent to 3 to 500% (mol basis) of the polymerization initiator concentration. A more preferred lower limit is 5% (mol basis), further preferably 8% (mol basis), further preferably 10% (mol basis), still more preferably 15% (mol basis), particularly preferably 20% (mol basis), particularly preferably 25% (mol basis), particularly preferably 30% (mol basis), and particularly preferably 35% (mol basis). A more preferred upper limit is 400% (mol basis), further preferably 300% (mol basis), still more preferably 200% (mol basis), and particularly preferably 100% (mol basis).

[0923] The decomposition agent of the polymerization initiator may be any compound capable of decomposing the polymerization initiator used, and is preferably at least one selected from the group consisting of sulfites, bisulfites, bromates, diimines, diimide salts, oxalic acid, oxalates, copper salts, and iron salts. Examples of the sulfite include sodium sulfite and ammonium sulfite. Examples of the copper salt include copper (II) sulfate, and examples of the iron salt include iron (II) sulfate.

[0924] The amount of the polymerization initiator decomposition agent added is 25 to 300 mass %, preferably 25 to 150 mass %, and more preferably 50 to 100 mass %, relative to the amount of the oxidizing agent combined with the polymerization initiator (redox initiator described below).

[0925] From the perspective of reducing the standard specific gravity, the amount of the polymerization initiator decomposition agent added is preferably an amount equivalent to 3 to 500% (mol basis) of the polymerization initiator concentration. The more preferred lower limit is 5% (mol basis), further preferably 8% (mol basis), further preferably 10% (mol basis), further preferably 13% (mol basis), and even more preferably 15% (mol basis). The more preferred upper limit is 400% (mol basis), further preferably 300% (mol basis), further more preferably 200% (mol basis), and even more preferably 100% (mol basis).

[0926] At least one selected from the group consisting of radical scavengers and decomposition agents of polymerization initiators is preferably added when the concentration of the TFE-based polymer formed in the aqueous medium is 5% by mass or more, more preferably 10% by mass or more.

[0927] Furthermore, it is preferred to add the TFE polymer when the concentration in the aqueous medium is 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0928] The adding step may be a step of continuously adding at least one selected from the group consisting of a radical scavenger and a decomposition agent of a polymerization initiator.

[0929] The continuous addition of at least one selected from the group consisting of radical scavengers and polymerization initiator decomposition agents is not, for example, a one-time addition but rather continuous or divided addition over time.

[0930] The above polymerization step may further include polymerizing tetrafluoroethylene in the presence of a nucleating agent.

[0931] The nucleating agent is preferably at least one selected from the group consisting of, for example, fluoropolyethers, nonionic surfactants, and chain transfer agents.

[0932] In this case, the polymerization step is preferably a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon-based surfactant and the nucleating agent to obtain a TFE-based polymer.

[0933] As the fluoropolyether, perfluoropolyether is preferred.

[0934] The fluoropolyether preferably has repeating units represented by formulae (1a) to (1d).

[0935] (-CFCF3-CF2-O-) n (1a)

[0936] (-CF2-CF2-CF2-O-) n (1b)

[0937] (-CF2-CF2-O-)n-(-CF2-O-) m (1c)

[0938] (-CF2-CFCF3-O-)n-(-CF2-O-) m (1d)

[0939] (In formulas (1a) to (1d), m and n are integers of 1 or greater.)

[0940] The fluoropolyether is preferably a fluoropolyether acid or a salt thereof. The fluoropolyether acid is preferably a carboxylic acid, a sulfonic acid, a sulfonamide, or a phosphonic acid, and more preferably a carboxylic acid. Among the fluoropolyether acids or salts thereof, a salt of a fluoropolyether acid is preferred, an ammonium salt of a fluoropolyether acid is more preferred, and an ammonium salt of a fluoropolyether carboxylic acid is even more preferred.

[0941] The fluoropolyether acid or its salt may have any chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Two or more types of fluorocarbon groups may be present in the molecule.

[0942] The fluoropolyether acid or its salt is preferably the following:

[0943] CF3-CF2-CF2-O(-CFCF3-CF2-O-) n CFCF3-COOH,

[0944] CF3-CF2-CF2-O(-CF2-CF2-CF2-O-) n -CF2-CF2COOH, or

[0945] HOOC-CF2-O(-CF2-CF2-O-)n-(-CF2-O-) m CF2COOH

[0946] (wherein m and n are the same as above.) or a salt thereof.

[0947] These structures were studied by Kasai in J. Appl. Polymer Sci., 57, 797 (1995). As disclosed therein, such fluoropolyethers may have a carboxylic acid group or its salt at one or both ends. Similarly, such fluoropolyethers may have a sulfonic acid or phosphonic acid group or its salt at one or both ends. Furthermore, fluoropolyethers having acid functional groups at both ends may have different groups at each end. In the case of monofunctional fluoropolyethers, the other end of the molecule is typically perfluorinated, but may also contain hydrogen or chlorine atoms.

[0948] Fluoropolyethers having acid groups at one or both ends have at least two ether oxygen groups, preferably at least four ether oxygen groups, and even more preferably at least six ether oxygen groups. Preferably, at least one of the fluorocarbon groups separating the ether oxygens has two or three carbon atoms, and more preferably, at least two of these fluorocarbon groups have two or three carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have two or three carbon atoms. Furthermore, preferably, the fluoropolyether has a total of at least 15 carbon atoms, for example, where the minimum value of n or n+m in the repeating unit structure is at least 5. Two or more fluoropolyethers having acid groups at one or both ends can be used in the method according to the present invention. Generally, the fluoropolyether can contain two or more compounds in various proportions within a molecular weight range relative to the average molecular weight, unless special considerations are taken when producing a single specific fluoropolyether compound.

[0949] The fluoropolyether preferably has a number average molecular weight of 800 g / mol or greater. Fluoropolyether acids or their salts may be difficult to disperse in aqueous media, so the number average molecular weight is preferably less than 6000 g / mol. More preferably, the fluoropolyether acid or its salt has a number average molecular weight of 800 to 3500 g / mol, and even more preferably 1000 to 2500 g / mol.

[0950] The amount of the fluoropolyether is preferably 5 to 3000 ppm, more preferably 5 to 2000 ppm, with respect to the aqueous medium. The lower limit is further preferably 10 ppm, and the upper limit is further preferably 100 ppm.

[0951] As the nonionic surfactant used as the nucleating agent, the above-mentioned nonionic surfactants can be mentioned, preferably non-fluorine-free nonionic surfactants. For example, as the above-mentioned nonionic surfactant, the following general formula (i) can be mentioned:

[0952] R3 -OA 1 -H(i)

[0953] (Where R 3 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, 1 is a polyoxyalkylene chain. ) is a compound shown.

[0954] R 3 The number of carbon atoms in R is preferably 10 to 16, more preferably 12 to 16. 3 When the number of carbon atoms of R is 18 or less, it is difficult to obtain good dispersion stability of the aqueous dispersion. 3 When the number of carbon atoms is greater than 18, the flow temperature is high and thus it is difficult to handle. 3 When the number of carbon atoms is less than 8, the surface tension of the aqueous dispersion becomes high, and the permeability and wettability are likely to decrease.

[0955] The polyoxyalkylene chain can be composed of ethylene oxide and propylene oxide. This polyoxyalkylene chain has an average repeating number of 5 to 20 ethylene oxide groups and an average repeating number of 0 to 2 propylene oxide groups, and is a hydrophilic group. The number of ethylene oxide units can have either a conventional broad or narrow unimodal distribution, or a broader or bimodal distribution achieved through blending. When the average repeating number of propylene oxide groups is greater than 0, the ethylene oxide and propylene oxide groups in the polyoxyalkylene chain can be arranged in blocks or randomly.

[0956] From the viewpoint of the viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain composed of an average repeating number of oxyethylene groups of 7 to 12 and an average repeating number of oxypropylene groups of 0 to 2 is preferred. 1 When the average number of propylene oxide groups is 0.5 to 1.5, low foaming properties are good and this is preferred.

[0957] More preferably R 3 (R')(R")HC-, wherein R' and R" are the same or different linear, branched or cyclic alkyl groups, and the total number of carbon atoms is at least 5, preferably 7 to 17. Preferably, at least one of R' or R" is a branched or cyclic hydrocarbon group.

[0958] Specific examples of the polyoxyethylene alkyl ether include C 13 H 27 -O-(C2H4O) 10 -H, C 12 H 25 -O-(C2H4O) 10 -H, C 10 H 21 CH(CH3)CH2-O-(C2H4O)9-H、C 13H 27 -O-(C2H4O)9-(CH(CH3)CH2O)-H, C 16 H 33 -O-(C2H4O) 10 -H、HC(C5H 11 )(C7H 15 )-O-(C2H4O)9-H, etc. Examples of commercially available products of the polyoxyethylene alkyl ethers include Genapol X080 (product name, manufactured by Clariant), Noigen TDS series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) exemplified by Noigen TDS-80 (trade name), Leocol TD series (manufactured by LION Corporation) exemplified by Leocol TD-90 (trade name), LIONOL (registered trademark) TD series (manufactured by LION Corporation), T-Det A series (manufactured by Harcros Chemicals) exemplified by T-Det A138 (trade name), and TERGITOL (registered trademark) 15S series (manufactured by Dow Chemical).

[0959] The nonionic surfactant is preferably a 2,6,8-trimethyl-4-nonanol ethoxylate having an average of about 4 to about 18 ethylene oxide units, a 2,6,8-trimethyl-4-nonanol ethoxylate having an average of about 6 to about 12 ethylene oxide units, or a mixture thereof. This type of nonionic surfactant is also commercially available as, for example, TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (all product names, manufactured by Dow Chemical).

[0960] In addition, the hydrophobic group of the nonionic surfactant may be any of an alkylphenol group, a linear alkyl group, and a branched alkyl group.

[0961] For example, polyoxyethylene alkylphenyl ether-based nonionic compounds include the following general formula (ii):

[0962] R 4 -C6H4-OA 2 -H(ii)

[0963] (Where R 4 is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms, 2 The compound represented by (a) is a polyoxyalkylene chain. Specific examples of the polyoxyethylene alkylphenyl ether-based nonionic compound include Triton (registered trademark) X-100 (product name, manufactured by Dow Chemical Co., Ltd.).

[0964] Examples of the nonionic surfactant include polyol compounds, and specifically, those described in International Publication No. 2011 / 014715.

[0965] Typical examples of polyol compounds include compounds having one or more sugar units as polyol units. The sugar unit may be modified so as to contain at least one long chain. Suitable polyol compounds containing at least one long chain portion include, for example, alkyl glycosides, modified alkyl glycosides, sugar esters, and combinations thereof. Examples of sugars include, but are not limited to, monosaccharides, oligosaccharides, and sorbitan. Examples of monosaccharides include, but are not limited to, pentose and hexose. Typical examples of monosaccharides include ribose, glucose, galactose, mannose, fructose, arabinose, and xylose. Examples of oligosaccharides include oligomers of 2 to 10 identical or different monosaccharides. Examples of oligosaccharides include, but are not limited to, sucrose, maltose, lactose, raffinose, and isomaltose.

[0966] Typically, sugars suitable for use as polyol compounds include five-membered ring compounds containing four carbon atoms and one heteroatom (usually oxygen or sulfur, preferably an oxygen atom), or six-membered ring compounds containing five carbon atoms and one heteroatom as described above, preferably an oxygen atom. These compounds further contain at least two or at least three hydroxyl groups (-OH groups) bonded to carbon ring atoms. Typically, to create an ether or ester bond between the long-chain residue and the sugar moiety, the sugar is modified so that at least one of the hydrogen atoms of the hydroxyl (and / or hydroxyalkyl) groups bonded to the carbon ring atoms is replaced with a long-chain residue.

[0967] The sugar polyol may contain one sugar unit or two or more sugar units. One sugar unit or two or more sugar units may be modified with a long chain moiety as described above. Specific examples of sugar polyol compounds include glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof.

[0968] Preferred types of polyol compounds are alkyl or modified alkyl glucosides. These types of surfactants contain at least one glucose moiety. Examples include:

[0969] [Chemistry 39]

[0970]

[0971] (wherein, x represents 0, 1, 2, 3, 4 or 5, R 1 and R 2 independently represents H or a long chain unit containing at least 6 carbon atoms, wherein R 1 and R 2At least one of which is not H). 1 and R 2 Typical examples of aliphatic alcohol residues include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, cetyl alcohol, heptadecanol, stearyl alcohol (stearyl alcohol), eicosanoic acid, and combinations thereof.

[0972] The above formula shows a specific example of an alkyl polyglycoside of glucose in the pyranose form, but it is understood that other sugars or sugars in different mirror isomer or diastereomeric forms of the same sugar may be used.

[0973] Alkyl glucosides can be obtained, for example, by the acid-catalyzed reaction of glucose, starch, or n-butyl glucoside with an aliphatic alcohol. In typical examples, mixtures of various alkyl glucosides can be obtained (Alkylpolygylcoside, Rompp, Lexikon Chemie, Version 2.0, Stuttgart / New York, Georg Thieme Verlag, 1999). Examples of aliphatic alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, cetyl alcohol, heptadecanol, stearyl alcohol (stearyl alcohol), eicosanoic acid, and combinations thereof. Alkyl glucosides are commercially available under the trade names GLUCOPON or DISPONIL from Cognis GmbH, Düsseldorf, Germany.

[0974] Other nonionic surfactants include bifunctional block copolymers supplied by BASF as the Pluronic (registered trademark) R series, tridecyl alcohol alkoxylates supplied by BASF Corporation as the Iconol (registered trademark) TDA series, and hydrocarbon-containing siloxane surfactants, preferably hydrocarbon surfactants. Here, when the above-mentioned hydrocarbon groups may be substituted with halogens such as fluorine, they are completely substituted with hydrogen atoms. Therefore, these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituent on the hydrocarbon group is hydrogen.

[0975] In addition, in the above-mentioned production method, in addition to the above-mentioned specific hydrocarbon-based surfactant and other compounds having surface active properties used as desired, additives for stabilizing the compounds can also be used. Examples of such additives include buffers, pH adjusters, stabilization aids, and dispersion stabilizers.

[0976] Preferred stabilizing agents include paraffin wax, fluorinated oils, fluorinated solvents, and silicone oils. Stabilizing agents may be used alone or in combination of two or more. Paraffin wax is more preferred. Paraffin wax can be liquid, semisolid, or solid at room temperature, and is preferably a saturated hydrocarbon with 12 or more carbon atoms. The melting point of paraffin wax is generally preferably 40-65°C, more preferably 50-65°C.

[0977] The amount of the stabilizing agent used is preferably 0.1 to 12% by mass, more preferably 0.1 to 8% by mass, based on the mass of the aqueous medium used. The stabilizing agent preferably has sufficient hydrophobicity and completely separates from the TFE-based polymer aqueous emulsion after the emulsion polymerization of TFE, without becoming a contaminating component.

[0978] In the above-mentioned production method, emulsion polymerization can be carried out by placing an aqueous medium, the above-mentioned hydrocarbon-based surfactant, monomers, and other additives as needed into a polymerization reactor, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of polymerization initiator to initiate the polymerization reaction. After the polymerization reaction begins, monomers, polymerization initiators, chain transfer agents, and the above-mentioned surfactants can be added additionally depending on the purpose. The above-mentioned hydrocarbon-based surfactant can be added after the polymerization reaction begins.

[0979] In the emulsion polymerization described above, the polymerization temperature and polymerization pressure are appropriately determined depending on the type of monomer used, the molecular weight of the target TFE-based polymer, and the reaction rate. Generally, 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.

[0980] The polymerization pressure is 0.05 MPaG to 10 MPaG. The polymerization pressure is more preferably 0.3 MPaG or higher, and even more preferably 0.5 MPaG or higher. The polymerization pressure is more preferably 5.0 MPaG or lower, and even more preferably 3.0 MPaG or lower.

[0981] Particularly, from the viewpoint of improving the yield, it is preferably 1.0 MPaG or higher, more preferably 1.2 MPaG or higher, further preferably 1.5 MPaG or higher, still more preferably 1.8 MPaG or higher, and particularly preferably 2.0 MPaG or higher.

[0982] In the emulsion polymerization described above, the hydrocarbon surfactant is preferably added when the concentration of the TFE polymer formed in the aqueous medium is less than 0.60 mass%. More preferably, the concentration is 0.50 mass% or less, even more preferably 0.36 mass% or less, still more preferably 0.30 mass% or less, even more preferably 0.20 mass% or less, and particularly preferably 0.10 mass% or less. It is most preferably added simultaneously with the start of polymerization. The above concentration is relative to the total concentration of the aqueous medium and the TFE polymer.

[0983] Furthermore, in the emulsion polymerization described above, the amount of the hydrocarbon surfactant at the start of polymerization is preferably 1 ppm or greater relative to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 10 ppm or greater, more preferably 50 ppm or greater, even more preferably 100 ppm or greater, and even more preferably 200 ppm or greater. The upper limit is not particularly limited, but is preferably 100,000 ppm, and more preferably 50,000 ppm. By setting the amount of the hydrocarbon surfactant at the start of polymerization within the above range, an aqueous dispersion having a smaller average primary particle size and superior stability can be obtained.

[0984] The polymerization initiator is not particularly limited 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, the polymerization can be initiated in a redox manner in combination with a reducing agent. The concentration of the polymerization initiator is appropriately determined based on the type of monomer, the molecular weight of the target TFE-based polymer, and the reaction rate.

[0985] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0986] The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, and for example, the following peroxides may be cited as representative substances: dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate; dialkyl peroxides such as di-tert-butyl peroxide; and di(ω-hydro-dodecafluoroheptanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleranoyl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide. peroxide, bis(perfluorononanoyl) peroxide, bis(ω-chloro-hexafluorobutyryl) peroxide, bis(ω-chloro-decafluorohexanoyl) peroxide, bis(ω-chloro-tetrafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydro-dodecafluoroheptanoyl-perfluorobutyryl-peroxide, bis(dichloropentafluorobutyryl) peroxide, bis(trichlorooctafluorohexanoyl) peroxide, bis(tetrachloroundecanoyl) peroxide, bis(pentachlorotetrafluorodecanoyl) peroxide, bis(undecachlorotriadecanoyl) peroxide, etc.

[0987] The oil-soluble radical polymerization initiator preferably does not contain a fluorine atom.

[0988] The water-soluble free radical polymerization initiator may be a known water-soluble peroxide, such as ammonium, potassium, or sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, or percarbonic acid, tert-butyl permaleate, or tert-butyl hydroperoxide. A reducing agent such as a sulfite or sulfite salt may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.

[0989] For example, when polymerization is carried out at a low temperature of 30°C or lower, it is preferred to use a redox initiator that combines an oxidizing agent and a reducing agent as a polymerization initiator. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, ceric ammonium nitrate, and bromates. Examples of the reducing agent include sulfites, bisulfites, bromates, diimides, and oxalic acid. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the sulfite include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferred to add a copper salt or an iron salt to the combination of the redox initiator. Examples of the copper salt include copper (II) sulfate, and examples of the iron salt include iron (II) sulfate.

[0990] As the redox initiator, preferably, the oxidizing agent is permanganic acid or a salt thereof, persulfate, manganese triacetate, cerium (IV) salt, or bromic acid or a salt thereof, and the reducing agent is dicarboxylic acid or a salt thereof, or diimine.

[0991] More preferably, the oxidizing agent is permanganic acid or a salt thereof, persulfate, or bromic acid or a salt thereof, and the reducing agent is dicarboxylic acid or a salt thereof.

[0992] Examples of the redox initiator include combinations of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, manganese triacetate / oxalic acid, manganese triacetate / ammonium oxalate, cerium ammonium nitrate / oxalic acid, and cerium ammonium nitrate / ammonium oxalate.

[0993] When a redox initiator is used, either the oxidizing agent or the reducing agent can be pre-charged into the polymerization vessel, followed by continuous or intermittent addition of the other to initiate polymerization. For example, when potassium permanganate / ammonium oxalate is used, it is preferred to charge ammonium oxalate into the polymerization vessel and continuously add potassium permanganate thereto.

[0994] In addition, in the present specification, when a redox initiator is described as "potassium permanganate / ammonium oxalate", it means a combination of potassium permanganate and ammonium oxalate. The same applies to other compounds.

[0995] As the redox initiator, it is preferable to use an oxidizing agent or reducing agent that can make the pH of the redox initiator aqueous solution be 4.0 or higher. The redox initiator aqueous solution is a 0.50 mass % aqueous solution of the oxidizing agent or a 0.50 mass % aqueous solution of the reducing agent.

[0996] That is, at least one of the 0.50 mass % aqueous solution of the oxidizing agent and the 0.50 mass % aqueous solution of the reducing agent may have a pH of 4.0 or higher, and preferably both of the 0.50 mass % aqueous solution of the oxidizing agent and the 0.50 mass % aqueous solution of the reducing agent have a pH of 4.0 or higher.

[0997] The pH of the redox initiator aqueous solution (0.50 mass % aqueous solution of the oxidizing agent or 0.50 mass % aqueous solution of the reducing agent) is more preferably 5.0 or higher, further preferably 5.5 or higher, and particularly preferably 6.0 or higher.

[0998] The redox initiator is particularly preferably a combination of an oxidizing agent which is a salt and a reducing agent which is a salt.

[0999] For example, the oxidizing agent as the 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.

[1000] The reducing agent for the salt is more preferably at least one selected from the group consisting of oxalates, malonates, succinates, glutarates, and bromates, further preferably oxalates, and particularly preferably ammonium oxalate.

[1001] Specifically, the redox initiator is preferably at least one selected from the group consisting of potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, manganese triacetate / ammonium oxalate, and ceric ammonium nitrate / ammonium oxalate, and more preferably at least one selected from the group consisting of potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, and ceric ammonium nitrate / ammonium oxalate.

[1002] By using a redox initiator in the polymerization step, the molecular weight of the resulting TFE-based polymer can be increased, thereby reducing SSG and enabling the production of a stretchable polymer.

[1003] Furthermore, by using a redox initiator in the polymerization step, the number of TFE polymer particles produced in the aqueous dispersion can be increased, and the yield of the TFE polymer can also be improved.

[1004] When a redox initiator is used, the oxidizing agent and the reducing agent may be added at once at the beginning of the polymerization, the reducing agent may be added at once and the oxidizing agent may be added continuously at the beginning of the polymerization, the oxidizing agent may be added at once and the reducing agent may be added continuously at the beginning of the polymerization, or both the oxidizing agent and the reducing agent may be added continuously.

[1005] When a redox initiator is used as the polymerization initiator, the amount of the oxidizing agent added is preferably 5 to 10,000 ppm, more preferably 10 to 1,000 ppm, and the amount of the reducing agent added is preferably 5 to 10,000 ppm, more preferably 10 to 1,000 ppm, relative to the aqueous medium.

[1006] When a redox initiator is used in the polymerization step, the polymerization temperature is preferably 100°C or lower, more preferably 95°C or lower, and even more preferably 90°C or lower. It is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher.

[1007] There are no particular restrictions, and the amount of the polymerization rate can be added once, successively, or continuously in the initial stage of polymerization to an amount that does not significantly reduce the polymerization rate (for example, a concentration of several ppm relative to water). The upper limit is the range in which the heat of the polymerization reaction can be removed from the device surface and the reaction temperature can be increased. The more preferred upper limit is the range in which the heat of the polymerization reaction can be removed from the device surface. More specifically, for example, it is preferably more than 1 ppm, more preferably more than 10 ppm, and further preferably more than 50 ppm relative to the aqueous medium. In addition, it is preferably less than 100,000 ppm, more preferably less than 10,000 ppm, and further preferably less than 5,000 ppm.

[1008] The aqueous medium is a reaction medium for polymerization and is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water and may contain water and a non-fluorinated organic solvent such as an alcohol, ether, or ketone and / or a fluorinated organic solvent having a boiling point of 40°C or less.

[1009] In the above-mentioned emulsion polymerization, the polymerization rate and molecular weight can be adjusted by further adding a known chain transfer agent according to the purpose.

[1010] Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate; and various halogenated hydrocarbons such as isopentane, methane, ethane, propane, isobutane, methanol, ethanol, isopropanol, acetone, various mercaptans, and carbon tetrachloride; and cyclohexane.

[1011] As a chain transfer agent, a bromine compound or an iodine compound can be used. As a polymerization method using a bromine compound or an iodine compound, for example, a method of polymerizing a fluorine monomer in an aqueous medium in the presence of a bromine compound or an iodine compound in a substantially oxygen-free state (iodine transfer polymerization method) can be cited. As a representative example of the bromine compound or iodine compound used, for example, the general formula:

[1012] R a I x Br y

[1013] (where x and y are integers from 0 to 2 and satisfy 1≤x+y≤2, R a A compound represented by a saturated or unsaturated fluorocarbon or chlorofluorocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom. By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer, functioning as a crosslinking point.

[1014] Examples of the iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodine-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodine-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodine-n-propane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, Br CF2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluoro-1-butene, 2-bromo-4-iodoperfluoro-1-butene, monoiodine and monobromine substitutions of benzene, diiodine and monobromine substitutions, and (2-iodineethyl) and (2-bromoethyl) substitutions, etc. These compounds can be used alone or in combination with each other.

[1015] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferably used in view of polymerization reactivity, crosslinking reactivity, and availability.

[1016] The amount of the chain transfer agent used is usually 1 to 50,000 ppm, preferably 1 to 20,000 ppm, based on the total amount of the fluorinated monomer supplied.

[1017] The chain transfer agent may be added to the reaction vessel all at once before the start of polymerization, may be added all at once after the start of polymerization, may be added in divided portions a plurality of times during polymerization, or may be added continuously during polymerization.

[1018] The above-mentioned production method can produce a TFE-based polymer aqueous dispersion. The above-mentioned TFE-based polymer aqueous dispersion generally comprises a TFE-based polymer, compound (1) and / or (2), and an aqueous medium. The solid content concentration of the TFE-based polymer aqueous dispersion is not limited, and can be, for example, 1.0 to 70% by mass. The above-mentioned solid content concentration is preferably 8.0% by mass or more, more preferably 10.0% by mass or more, and preferably 60.0% by mass or less, more preferably 50.0% by mass or less.

[1019] In the above-mentioned production method, the adhesion amount is preferably 3.0 mass% or less, more preferably 2.0 mass% or less, further preferably 1.0 mass% or less, more preferably 0.8 mass% or less, still more preferably 0.7 mass% or less, and particularly preferably 0.6 mass% or less, based on the finally obtained TFE-based polymer.

[1020] The precipitation in step (B) can be performed by a known method.

[1021] Under the situation that the aqueous dispersion of above-mentioned TFE-based polymer is precipitated, usually use water that polymer emulsion etc. is diluted so that polymer concentration is 10~25 mass % (preferred polymer concentration is 10~20 mass %), according to the circumstances, after pH is adjusted to neutrality or alkaline, in the container with stirrer, carry out stirring more violently than the stirring in the reaction.Above-mentioned precipitation can stir when adding inorganic salts, hydrochloric acid, sulfuric acid, nitric acid such as water-soluble organic compounds, saltpetre, ammonium carbonate etc. as precipitating agent.In addition, above-mentioned precipitation can use online mixer etc. to carry out continuously.

[1022] As precipitation method, be preferably selected from at least one precipitation method in the group consisting of the precipitation method based on stirring, ultrasonic precipitation method, the precipitation method of use ultrafine bubble, the precipitation method of use alkali precipitation method, the precipitation method of use acid, the precipitation method of use oxidant, the precipitation method of use organic solvent and the precipitation method of use free radical initiator.In addition, in the manufacture method of the present invention, also preferably when stirring aqueous dispersion, use at least one precipitation method in the group consisting of the precipitation method based on stirring, the precipitation method of use ultrafine bubble, the precipitation method of use alkali, the precipitation method of use acid, the precipitation method of use oxidant, the precipitation method of use organic solvent and the precipitation method of use free radical initiator to make non-melt processability TFE based polymer precipitate.

[1023] As described later, when heat-treating at low temperatures, can not fully reduce the content of the fluorochemical with hydrophilic group in the wet powder, thus, can not obtain the non-melt processability TFE based polymer that can be extruded with stable extrusion pressure sometimes.On the other hand, when heat treatment temperature is too high, though can reduce the content of the fluorochemical with hydrophilic group in the wet powder, the extrusion pressure of obtained non-melt processability TFE based polymer becomes too high.By heat-treating at low temperatures and utilizing said method to precipitate, can take into account the sufficient removal of the fluorochemical with hydrophilic group and the stabilization of low extrusion pressure well.

[1024] The temperature of the aqueous dispersion for precipitating the non-melt-processability TFE-based polymer may be 3 to 95°C, 5°C or higher, 10°C or higher, 85°C or lower, 75°C or lower, or 60°C or lower.

[1025] In the precipitation method based on stirring, aqueous dispersion is stirred vigorously to the degree that non-melt processability TFE-based polymer particles are precipitated.Stirring can be carried out using the container of for example band stirrer.Utilize the precipitation based on the precipitation method of stirring and can use in-line mixer etc. to carry out continuously.

[1026] In the ultrasonic precipitation method, strong ultrasonic waves of a degree that causes precipitation of non-melt-processability TFE-based polymer particles are irradiated onto an aqueous dispersion.

[1027] The output power of the ultrasound is preferably 100 W or more, more preferably 200 W or more, further preferably 300 W or more, particularly preferably 400 W or more, and particularly preferably 500 W or more, and is preferably 3000 W or less, more preferably 1000 W or less, and further preferably 800 W or less.

[1028] The frequency of the ultrasonic wave is preferably 15 kHz or higher, more preferably 20 kHz or higher, further preferably 25 kHz or higher, particularly preferably 30 kHz or higher, and particularly preferably 40 kHz or higher, and is preferably 100 kHz or lower, more preferably 80 kHz or lower, and further preferably 50 kHz or lower.

[1029] The ultrasonic irradiation time is preferably 60 seconds or longer, more preferably 300 seconds or longer, and preferably 20 minutes or shorter.

[1030] Ultrasonic irradiation can be performed using a commercially available ultrasonic generator, such as a commercially available ultrasonic emitting device (eg, ultrasonic homogenizer), an ultrasonic transmitter, a circulating ultrasonic irradiator, an ultrasonic vibrator, or an ultrasonic cleaner.

[1031] Specific methods of irradiating with ultrasonic waves include, for example, a method in which the nozzle of an ultrasonic homogenizer is immersed in the aqueous dispersion, a method in which a submersible ultrasonic vibrator is immersed in a container containing the TFE-based polymer aqueous dispersion, a method in which the container containing the TFE-based polymer aqueous dispersion is introduced into an ultrasonic cleaning apparatus previously filled with an aqueous medium, etc., a method in which the TFE-based polymer aqueous dispersion is introduced into a tank-shaped ultrasonic cleaning apparatus or ultrasonic generator, a method in which the TFE-based polymer aqueous dispersion is introduced into a tank equipped with a rod-shaped ultrasonic irradiator, etc. It is also preferred to irradiate the aqueous dispersion with ultrasonic waves while stirring the aqueous dispersion.

[1032] In the precipitation method using ultrafine bubbles, ultrafine bubbles are generated in an aqueous dispersion in an amount sufficient to cause precipitation of non-melt-processable TFE-based polymer particles. Ultrafine bubbles are defined as bubbles having a diameter of 1 μm or less. Ultrafine bubbles can be generated, for example, by irradiating the aqueous dispersion with ultrasonic waves to induce cavitation. It is also preferred that the aqueous dispersion producing the ultrafine bubbles be stirred.

[1033] The time for the treatment with ultrafine bubbles is preferably 60 seconds or longer, more preferably 300 seconds or longer, and preferably 20 minutes or shorter.

[1034] In the precipitation method using an alkali, an alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia can be used. As the ammonia, ammonium bicarbonate or ammonium carbonate is preferred. As the alkali, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia is preferred, with sodium hydroxide being more preferred. It is also preferred to stir the alkali-containing aqueous dispersion.

[1035] As the fluorochemical with hydrophilic group, when the aqueous dispersion containing the fluorochemical with anionic group is used to precipitate in the case of alkali, the anionic group of fluorochemical is converted to salt form and the water-soluble improvement of fluorochemical is made, therefore, there is the advantage of easily removing fluorochemical from wet powder by the cleaning of the wet powder obtained by precipitation.The fluorochemical with the anionic group of salt form that also can remain in the wet powder after cleaning is difficult to volatilize, therefore there is the tendency that is also difficult to remove by the thermal treatment of wet powder, but if acid is used to clean wet powder before thermal treatment in advance, the content of fluorochemical can be further reduced smoothly.Therefore, after using alkali to precipitate, using acid to clean the obtained wet powder and to heat-treat the wet powder after cleaning is also one of preferred embodiment.

[1036] In the precipitation method using acid, organic acid or inorganic acid can be used. As acid, from the aspect that is difficult to remain during heat treatment, preferred inorganic acid, particularly preferably at least one selected from the group consisting of nitric acid, sulfuric acid, oleum, perchloric acid and hydrochloric acid, more preferably at least one selected from the group consisting of nitric acid, sulfuric acid and hydrochloric acid. As the above-mentioned organic acid, succinic acid, oxalic acid, citric acid, trifluoroacetic acid etc. can be enumerated. The addition amount of acid is not limited, and can be appropriately set according to the pH value of the aqueous dispersion. Also preferably, the aqueous dispersion containing acid is stirred.

[1037] In the precipitation method using an oxidant, at least one selected from the group consisting of an inorganic acid and its salt can be used. As an inorganic acid, nitrous acid, nitric acid, sulfurous acid, sulfuric acid, persulfuric acid, hydrochloric acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hydrofluoric acid, bromic acid, iodic acid, phosphoric acid, boric acid, chromic acid, nikrom nickel-chromium heat-resistant alloy acid, permanganic acid, etc. can be enumerated. As the salt of an inorganic acid, sodium salts, potassium salts, ammonium salts, magnesium salts, calcium salts, aluminum salts, silver salts, etc. can be enumerated. As an oxidant, at least one selected from the group consisting of nitric acid and its salt and perchloric acid and its salt is more preferably selected from, at least one selected from the group consisting of nitrate and perchlorate is further preferably selected from, at least one selected from the group consisting of sodium nitrate, potassium nitrate, ammonium nitrate and ammonium perchlorate is particularly preferably selected from. Two or more oxidants can be used in combination. For example, an inorganic acid and an inorganic acid salt can be used in combination, or nitric acid and a nitrate (such as sodium nitrate, ammonium nitrate, etc.) can be used in combination. Also preferably, the aqueous dispersion containing an oxidant is stirred.

[1038] The amount of the oxidant added is preferably 0.01 to 20% by mass, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, more preferably 10% by mass or less, further preferably 5% by mass or less relative to the non-melt-processable TFE-based polymer in the aqueous dispersion. In one embodiment, the non-melt-processable TFE-based polymer is precipitated by adding the oxidant to the aqueous dispersion and stirring.

[1039] In the precipitation method using an organic solvent, for example, the following organic solvents can be used.

[1040] alcohol;

[1041] Carboxylic acids such as acetic acid, propionic acid, ethoxyacetic acid, and valeric acid;

[1042] Esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, and dimethyl carbonate;

[1043] Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and 3-methyl-2-cyclopentenone;

[1044] Aromatic hydrocarbons such as benzene, toluene, and xylene;

[1045] Ethers such as diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and 1,2-dimethoxyethane.

[1046] As the organic solvent, alcohols are preferred. The alcohol may be any of monohydric, dihydric, and trihydric alcohols. Monohydric alcohols are preferred. The number of carbon atoms in the alcohol is preferably 2 to 7, more preferably 3 or more, more preferably 5 or less, and even more preferably 4 or less. As the organic solvent, at least one selected from the group consisting of methanol, 1-propanol, 2-propanol, 2-butanol, and 1-pentanol is preferred, at least one selected from the group consisting of 1-propanol, 2-propanol, 2-butanol, and 1-pentanol is more preferred, and at least one selected from the group consisting of 1-propanol, 2-butanol, and 1-pentanol is even more preferred.

[1047] The addition of organic solvent is preferably the weight suitable above 1.0 quality % with respect to the non-melt processability TFE based polymer in the aqueous dispersion.The amount of the organic solvent that is used for precipitating is more preferably more than 5.0 quality %, further preferably more than 10 quality %, particularly preferably more than 20 quality %, be preferably with 50 times of suitable weight below amount, more preferably with 10 times of suitable weight below amount, further preferably with 5 times of suitable weight below amount.Also preferably the aqueous dispersion that contains organic solvent is stirred.

[1048] In the precipitation method using free radical initiator, water-soluble free radical initiator can be suitably used.As free radical initiator, the combination of organic peroxide, inorganic peroxide, organic azo compound, oxidant and reducing agent etc. can be enumerated, preferably at least one in the group consisting of the combination of inorganic peroxide, organic peroxide and oxidant and reducing agent is selected from.In one embodiment, in aqueous dispersion, add free radical initiator, aqueous dispersion is heated to more than the decomposition temperature of free radical initiator, non-melt processability TFE based polymer is precipitated.Also preferably the aqueous dispersion containing free radical initiator is stirred.

[1049] As the inorganic peroxide, a water-soluble inorganic peroxide is preferred. Examples of the inorganic peroxide include hydrogen peroxide, perchlorates, perborates, perphosphates, percarbonates, and persulfates, with persulfates being preferred. As the persulfate, at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate is preferred, with ammonium persulfate being more preferred.

[1050] As the organic peroxide, a water-soluble organic peroxide is preferred. Examples of the organic peroxide include peroxydicarbonates such as disuccinic acid peroxide and diglutaric acid peroxide.

[1051] As the radical initiator, an oxidizing agent and a reducing agent may be used in combination. By using the oxidizing agent and the reducing agent in combination, radicals can be generated from the radical initiator by the redox reaction between the oxidizing agent and the reducing agent, thereby lowering the temperature during the heat treatment.

[1052] Examples of oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, and cerium ammonium nitrate. 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. In order to increase the decomposition rate of the oxidizing agent, it is also preferable to add copper salts or iron salts. Examples of copper salts include copper (II) sulfate, and examples of iron salts include iron (II) sulfate.

[1053] The heating temperature of the aqueous dispersion containing the radical initiator is not particularly limited as long as it is a temperature (decomposition temperature) at which the radical initiator decomposes to generate radicals. It is preferably 35°C or higher, more preferably 40°C or higher, further preferably 45°C or higher, particularly preferably 50°C or higher, preferably 120°C or lower, more preferably 110°C or lower, further preferably 100°C or lower, and particularly preferably 90°C or lower.

[1054] In the production method of the present invention, it is preferred that the wet powder is obtained by recovering the precipitate produced by precipitation of the non-melt-processability TFE-based polymer and then washing the wet powder. The washing may be performed once or twice or more.

[1055] The cleaning method is preferably at least one cleaning method selected from the group consisting of a cleaning method using stirring, an ultrasonic cleaning method, a cleaning method using ultrafine bubbles, a cleaning method using an alkali, a cleaning method using an acid, and a cleaning method using a radical initiator.

[1056] As described later, when heat-treating at relatively low temperatures, can not fully reduce the content of the fluorochemical with hydrophilic group in the wet powder, thus, can not obtain the non-melt processability TFE based polymer that can be extruded with stable extrusion pressure sometimes.On the other hand, when heat treatment temperature is too high, although can reduce the content of the fluorochemical with hydrophilic group in the wet powder, the extrusion pressure of obtained non-melt processability TFE based polymer becomes too high.By heat-treating at relatively low temperatures and utilizing said method to precipitate, can take into account the sufficient removal and the stabilization of low extrusion pressure of the fluorochemical with hydrophilic group well.And then, by heat-treating at relatively low temperatures, utilizing said method to precipitate and utilizing said method to clean, can more easily take into account the sufficient removal and the stabilization of low extrusion pressure of the fluorochemical with hydrophilic group well.

[1057] The temperature during washing of the wet powder may be 3 to 95° C., 5° C. or higher, or 10° C. or higher, or 85° C. or lower, 75° C. or lower, or 60° C. or lower.

[1058] In the stirring washing method, the wet powder is placed in water and stirred. Stirring can be performed using, for example, a container equipped with a stirrer. Washing is preferably performed multiple times. When performing multiple washes, the final wash is preferably performed at 30°C or below.

[1059] In ultrasonic cleaning, the wet powder is placed in a liquid and ultrasonic waves are applied to the liquid. Examples of the liquid include water and alcohol. The alcohol is preferably at least one selected from the group consisting of methanol, 1-propanol, 2-propanol, 2-butanol, and 1-pentanol, with methanol being more preferred.

[1060] The output power of the ultrasound is preferably 100 W or more, more preferably 200 W or more, further preferably 300 W or more, particularly preferably 400 W or more, particularly preferably 500 W or more, preferably 3000 W or less, more preferably 1000 W or less, further preferably 800 W or less.

[1061] The frequency of the ultrasonic wave is preferably 15 kHz or higher, more preferably 20 kHz or higher, further preferably 25 kHz or higher, particularly preferably 30 kHz or higher, particularly preferably 40 kHz or higher, preferably 100 kHz or lower, more preferably 80 kHz or lower, further preferably 50 kHz or lower.

[1062] The ultrasonic irradiation time is preferably 60 seconds or longer, more preferably 300 seconds or longer, preferably 180 minutes or shorter, more preferably 150 minutes or shorter, further preferably 120 minutes or shorter, and particularly preferably 20 minutes or shorter.

[1063] Ultrasonic irradiation can be performed using a commercially available ultrasonic generator, such as a commercially available ultrasonic emitting device (eg, ultrasonic homogenizer), an ultrasonic transmitter, a circulating ultrasonic irradiator, an ultrasonic vibrator, or an ultrasonic cleaner.

[1064] Specific methods for irradiating powders and liquids with ultrasonic waves include, for example, a method in which the nozzle portion of an ultrasonic homogenizer is immersed in an aqueous dispersion, a method in which an immersion-type ultrasonic vibrator is immersed in a container into which a liquid is introduced and irradiation is performed, a method in which a container containing a liquid is introduced into an ultrasonic cleaner pre-filled with an aqueous medium and irradiation is performed, a method in which a liquid is introduced into a tank-shaped ultrasonic cleaner or an ultrasonic generator and irradiation is performed, a method in which a liquid is introduced into a tank having a rod-shaped ultrasonic irradiation body and irradiation is performed, and the like.

[1065] In the ultrafine bubble cleaning method, wet powder is placed in water to generate ultrafine bubbles in the water. Ultrafine bubbles are defined as those with a diameter of 1 μm or less. Ultrafine bubbles can be generated by, for example, irradiating water with ultrasonic waves to induce cavitation.

[1066] The cleaning time by ultrafine bubbles is preferably 60 seconds or longer, more preferably 300 seconds or longer, and preferably 20 minutes or shorter.

[1067] In the cleaning method using an alkali, an alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia can be used. As the ammonia, ammonium bicarbonate or ammonium carbonate is preferred. As the alkali, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia is preferred, with sodium hydroxide being more preferred.

[1068] As a fluorochemical compound with a hydrophilic group, when a wet powder containing a fluorochemical compound with an anionic group is precipitated with an alkali, the anionic group of the fluorochemical compound is converted to a salt form and the water solubility of the fluorochemical compound is improved. Therefore, there is an advantage that the fluorochemical compound can be easily removed from the wet powder by cleaning the obtained wet powder. The fluorochemical compound with an anionic group in the form of a salt that also remains in the wet powder after cleaning is difficult to volatilize, and therefore has a tendency to be difficult to remove by heat treatment of the wet powder. However, if the wet powder is cleaned with an acid in advance before heat treatment, the content of the fluorochemical compound can be further smoothly reduced. Therefore, it is also one of the preferred embodiments to clean the wet powder with an alkali, then clean the wet powder with an acid, and heat-treat the cleaned wet powder.

[1069] In the cleaning method using acid, organic acid or inorganic acid can be used. From the aspect of being difficult to remain during heat treatment, inorganic acid is preferred, particularly preferably at least one selected from the group consisting of nitric acid, sulfuric acid, fuming sulfuric acid, perchloric acid and hydrochloric acid, more preferably at least one selected from the group consisting of nitric acid, sulfuric acid and hydrochloric acid. As the above-mentioned organic acid, succinic acid, oxalic acid, citric acid, trifluoroacetic acid, etc. can be mentioned. The amount of acid added is not limited and can be appropriately set according to the pH of the water containing the powder. In one embodiment, the wet powder and acid are put into water, and the water is stirred to perform cleaning.

[1070] In cleaning methods using a free radical initiator, a water-soluble free radical initiator can be suitably used. Examples of free radical initiators include organic peroxides, inorganic peroxides, organic azo compounds, and combinations of oxidizing agents and reducing agents. Preferably, at least one of the following is selected from the group consisting of inorganic peroxides, organic peroxides, and combinations of oxidizing agents and reducing agents. In one embodiment, the wet powder and the free radical initiator are placed in water, and the water is heated to a temperature above the decomposition temperature of the free radical initiator and stirred to perform cleaning.

[1071] As the radical initiator used for cleaning, there can be used any radical initiator that can be used in the precipitation method using a radical initiator.

[1072] The heating temperature of the water is not particularly limited as long as it is above the temperature at which the radical initiator decomposes to generate free radicals (decomposition temperature), but is preferably above 35°C, more preferably above 40°C, further preferably above 45°C, particularly preferably above 50°C, preferably below 120°C, more preferably below 110°C, further preferably below 100°C, and particularly preferably below 90°C.

[1073] In the production method of the present invention, it is preferred that the wet powder be washed and then subjected to heat treatment. The heat treatment may also be performed as step (C).

[1074] The moisture content of the heat-treated wet powder is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 150% by mass or less, more preferably 100% by mass or less, relative to the wet powder.

[1075] The temperature of the heat treatment is preferably 10 to 280°C. The temperature of the heat treatment may be 100°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, 150°C or higher, or 160°C or higher. The temperature of the heat treatment may be 230°C or lower, 210°C or lower, 200°C or lower, 190°C or lower, 185°C or lower, or 180°C or lower. In the production method of the present invention, it is preferred to perform the heat treatment at a relatively low temperature. By performing the heat treatment at a relatively low temperature, it is possible to produce a non-melt-processable TFE-based polymer in which the content of the fluorine-containing compound having a hydrophilic group is reduced and which can be extruded at a low extrusion pressure and a stable extrusion pressure.

[1076] The heat treatment time is preferably 5 to 3000 minutes. The heat treatment time may be 10 minutes or longer, 15 minutes or longer, 20 minutes or longer, 30 minutes or longer, 50 minutes or longer, 100 minutes or longer, 150 minutes or longer, or 200 minutes or longer. The heat treatment time may be 2500 minutes or shorter, or 2000 minutes or shorter. In the production method of the present invention, it is preferred to perform the heat treatment at a relatively low temperature for a relatively long time.

[1077] The heat treatment may be performed in air. Alternatively, the heat treatment in an oxygen-rich gas or an ozone-containing gas can further promote the reduction of the content of the fluorine-containing compound having a hydrophilic group.

[1078] As the method for heat treatment, preferably: make hot blast contact wet powder and carry out heat treatment method or heat wet powder in the presence of water vapor and carry out heat treatment method.If heat treatment is carried out at relatively low temperature, the content of the fluorochemical with hydrophilic group in the wet powder can not fully reduce, thus, sometimes can not obtain the non-melt processable TFE based polymer that can carry out extrusion molding with stable extrusion pressure.On the other hand, when the heat treatment temperature is too high, although the content of the fluorochemical with hydrophilic group in the wet powder can be reduced, the extrusion pressure of the non-melt processable TFE based polymer obtained becomes too high.By making the wet powder carry out heat treatment and use hot blast or water vapor to carry out heat treatment in the above-mentioned temperature range, can take into account the sufficient removal of the fluorochemical with hydrophilic group and the stabilization of low extrusion pressure.

[1079] Heat treatment using hot air can be performed by blowing hot air onto the wet powder. In one embodiment, the wet powder is placed in a container with a permeable bottom and / or sides, and hot air is blown onto the placed wet powder. In another embodiment, the wet powder is placed in a dryer and blown onto the wet powder by circulating hot air within the dryer.

[1080] The wind speed of the hot air blown to the wet powder can be 0.01 m / s or higher, 0.03 m / s or higher, 0.05 m / s or higher, 0.10 m / s or higher, 0.20 m / s or higher, 0.30 m / s or higher, or 0.40 m / s or higher. Alternatively, the wind speed of the hot air blown to the wet powder can be 10 m / s or lower, 5.0 m / s or lower, 3.0 m / s or lower, 2.0 m / s or lower, or 1.0 m / s or lower.

[1081] The treatment time in the heat treatment method of placing the wet powder in a container with an air-permeable bottom and / or side surfaces and blowing hot air on the arranged wet powder (sometimes referred to as "ventilation drying treatment" in the present invention) can be more than 5 minutes, more than 10 minutes, more than 15 minutes, more than 20 minutes, more than 30 minutes, more than 40 minutes, more than 50 minutes, more than 60 minutes or more than 80 minutes, and can be less than 300 minutes or less than 200 minutes.

[1082] The temperature of the hot air blown onto the wet powder is as described above as the heat treatment temperature. The treatment temperature (hot air temperature) during the ventilation drying process may be higher than 150°C, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, or 180°C or higher. Alternatively, the treatment temperature (hot air temperature) during the ventilation drying process may be lower than 260°C, lower than 235°C, lower than 230°C, lower than 225°C, lower than 220°C, lower than 215°C, or lower than 210°C.

[1083] In the ventilation drying process, for example, the treatment temperature (hot air temperature) can be set to greater than 250°C and less than 280°C, and the treatment time can be set to less than 50 minutes. Alternatively, the treatment temperature (hot air temperature) can be set to greater than 200°C and less than 250°C, and the treatment time can be set to less than 100 minutes. Alternatively, the treatment temperature (hot air temperature) can be set to greater than 150°C and less than 200°C, and the treatment time can be set to less than 200 minutes.

[1084] The wind speed of the hot air during the ventilation drying process may be 0.01 m / s or more, 0.03 m / s or more, 0.05 m / s or more, or 0.10 m / s or more. Alternatively, the wind speed of the hot air during the ventilation drying process may be 10 m / s or less, 5.0 m / s or less, 3.0 m / s or less, 2.0 m / s or less, or 1.0 m / s or less.

[1085] When an electric furnace is used in the heat treatment process, the amount of gas, air or water vapor supplied to the electric furnace, the amount of gas, air or water vapor circulated in the electric furnace, and the amount of gas, air or water vapor discharged outside the electric furnace can be adjusted.

[1086] The ratio of the amount of gas, air or water vapor discharged from the electric furnace to the amount circulating in the electric furnace can be more than 3 volume % , more than 5 volume % or more than 10 volume %, and can be less than 95 volume %, less than 80 volume % or less than 75 volume %.

[1087] The ratio of the amount of gas, air or water vapor exhausted from the electric furnace during the ventilation drying process to the amount circulating in the electric furnace can be 3% by volume or more, 5% by volume or more or 10% by volume or less, and can be 50% by volume or less, 40% by volume or less or 30% by volume or less.

[1088] The ratio of the amount of gas, air or water vapor exhausted from the electric furnace in the hot air circulation drying process to the amount circulating in the electric furnace can be more than 10% by volume, more than 20% by volume or more than 30% by volume, and can be less than 95% by volume, less than 80% by volume or less than 75% by volume.

[1089] When the heat treatment temperature is greater than 200°C, the ratio of the amount of gas, air or water vapor discharged from the electric furnace to the amount circulating in the electric furnace can be more than 3 volume %, more than 5 volume % or more than 10 volume %, and can be less than 50 volume %, less than 40 volume % or less than 30 volume %.

[1090] When the heat treatment temperature is below 200°C, the ratio of the amount of gas, air or water vapor discharged from the electric furnace to the amount circulating in the electric furnace can be more than 10% by volume, more than 20% by volume or more than 30% by volume, and can be less than 95% by volume, less than 80% by volume or less than 75% by volume.

[1091] The treatment time in the heat treatment method in which the wet powder is placed in a dryer and hot air is blown thereon by circulating hot air in the dryer (sometimes referred to as "hot air circulation drying treatment" in the present invention) can be more than 120 minutes, more than 180 minutes, more than 240 minutes or more than 300 minutes, and can be less than 1500 minutes or less than 1200 minutes.

[1092] The temperature of the hot air blown to the wet powder is as described above as the temperature for the heat treatment. Furthermore, the treatment temperature (hot air temperature) in the hot air circulation drying process may be greater than 150°C, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, or 180°C or higher, and may be 235°C or lower, 230°C or lower, 225°C or lower, 220°C or lower, 215°C or lower, or 210°C or lower.

[1093] The wind speed of the hot air in the hot air circulation drying process may be 0.10 m / s or more, 0.50 m / s or more, or 1.0 m / s or more, and may be 10 m / s or less, or 5.0 m / s or less.

[1094] Heat treatment can be performed by placing the wet powder in a container with air permeable bottom and / or side surfaces. The container with air permeable bottom and / or side surfaces can withstand the heat treatment temperature and is preferably made of metal such as stainless steel.

[1095] As a container having a breathable bottom and / or side surfaces, a tray (basin) having a breathable bottom and / or side surfaces is preferred, and a tray having a mesh bottom and / or side surfaces (mesh tray) is more preferred. The mesh is preferably a woven mesh or a perforated mesh. Examples of weaving methods for the woven mesh include plain weave, twill weave, flat fold weave, and diagonal fold weave. Furthermore, a combination of a mesh and a fabric is also possible.

[1096] The fabric can be in the form of a perforated pan lining used in tray drying in an oven, or a continuous belt running within the oven. In the case of a continuous belt, the process is continuously implemented, that is, the coagulum is continuously prevented at one end of the belt path, and the purified TFE-based polymer fine powder is continuously removed from the opposite end of the belt path. Here, the shallow layer of the coagulum is continuously exposed to heated air while moving along the path from one end to the opposite end. In either form, the fabric serves as a direct support for the coagulum and can be reused for additional polymer purification.

[1097] The fabric can be of any structure, for example, a knitted, spunbonded, or woven fabric that provides the required dimensional integrity depending on the fabric's intended form. In the case of knitted or woven fabrics, the fabric is made of yarn, while in the case of spunbonded structures, it is generally made of fibers. Depending on the situation, the yarns or fibers comprising the fabric pass through the heated air during the refining stage, but openings are provided between the yarns or fibers that allow the TFE-based polymer aggregates / fine powder particles to be retained (i.e., the TFE-based polymer fine powder does not pass through). To retain the TFE-based polymer fine powder, the openings in the fabric must be small, but they must also be large enough to allow the heated air and evaporated contaminants to pass through at a sufficient rate during refining with a moderate hot air contact time.

[1098] The mesh size of the net is preferably 2000 μm or less (10 mesh or more according to the ASTM standard), more preferably 595 μm or less (30 mesh or more), further preferably 297 μm or less (50 mesh or more), still more preferably 177 μm or less (80 mesh or more), particularly preferably 149 μm or less (100 mesh or more), and particularly preferably 74 μm or less (200 mesh or more). Furthermore, it is preferably 25 μm or more (500 mesh or less).

[1099] When the mesh is a punched mesh, the opening ratio is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, and preferably 95% or less.

[1100] The amount of wet powder is preferably 10 g / cm 2 Below, more preferably 8g / cm 2 Below, more preferably 5g / cm 2 Below, particularly preferably 3 g / cm 2 Below, preferably 0.01 g / cm 2 More preferably, 0.05 g / cm 2 More preferably, 0.1 g / cm 2 above.

[1101] Heat treatment using water vapor can be performed by blowing high-temperature steam onto the wet powder. In one embodiment, the wet powder is placed in a container with a permeable bottom and / or side surfaces, and high-temperature steam is blown onto the placed wet powder.

[1102] The heat treatment using water vapor can be performed under normal pressure or under pressure. The pressure when performing the heat treatment using water vapor can be 0.10 to 4.0 MPa. The pressure of the heat treatment under pressure can be greater than 0.10 MPa and can be 0.2 MPa or less.

[1103] Heat treatment using steam may also be performed under reduced pressure. The pressure of heat treatment under reduced pressure may be less than 0.10 MPa or 0.09 MPa or less, and may be 0.01 MPa or more.

[1104] The treatment time in the heat treatment using water vapor may be 5 minutes or longer, 10 minutes or longer, 15 minutes or longer, 30 minutes or longer, or 40 minutes or longer, and may be 10 hours or shorter, 8 hours or shorter, 6 hours or shorter, or 4 hours or shorter.

[1105] The temperature of the water vapor blown onto the wet powder is as described above as the temperature for the heat treatment. Furthermore, the treatment temperature (water vapor temperature) in the heat treatment using water vapor may be 100° C. or higher, 120° C. or higher, 140° C. or higher, 160° C. or higher, or 170° C. or higher, and may be 350° C. or lower, 300° C. or lower, 250° C. or lower, 230° C. or lower, or 210° C. or lower.

[1106] The amount of heating steam generated in the heat treatment using water vapor can be 1 kg / h or more, 3 kg / h or more, 5 kg / h or more, or 10 kg / h or less, and can be 500 kg / h or less, 300 kg / h or less, 100 kg / h or less, 50 kg / h or less, or 30 kg / h or less.

[1107] Heat treatment can be performed using an electric furnace or a steam furnace. For example, heat treatment can be performed using a parallel flow box furnace, a ventilated box furnace, a ventilated conveyor furnace, a tunnel furnace, a belt furnace, a turbine vertical furnace, a radiant conveyor furnace, a fluidized bed furnace, a ventilated rotary furnace, a trough stirring furnace, a multi-stage disc furnace, a vacuum furnace, a cylindrical furnace, a vibration furnace, a freezing furnace, a drum furnace, a trough furnace, an inverted cone furnace, an extrusion furnace, a steam heating tube bundle rotary furnace, an infrared furnace, a superheated steam furnace, a high-frequency furnace, a microwave furnace, a stirring furnace, an airflow furnace, a hot air circulation furnace, or a steam furnace corresponding to the above (a device with the electric furnace in the device name of each of the above furnaces replaced by a steam furnace).

[1108] It is also preferred to dry the wet powder by heat treatment. When the wet powder is heated at normal pressure or under pressure in the presence of water vapor, the wet powder is generally not sufficiently dried. Therefore, it is preferred to dry the wet powder after heat treatment to obtain a non-melt-processable TFE-based polymer powder.

[1109] By heat-treating the wet powder or heat-treating and drying it, a non-melt-processability TFE-based polymer powder having a water content of 0.01% by mass or less or 0.005% by mass or less relative to the wet powder can be obtained.

[1110] In step (C), the drying is typically performed using vacuum, high-frequency, hot air, or other methods while maintaining the wet powder in a non-flowing state, preferably a static state. Friction between powders, especially at high temperatures, often adversely affects fine powders of TFE-based polymers. This is because particles composed of such TFE-based polymers readily fibrillate even when subjected to small shear forces, losing their originally stable particle structure.

[1111] From the perspective of reducing extrusion pressure, the drying temperature is preferably 300°C or lower, more preferably 250°C or lower, even more preferably 230°C or lower, still more preferably 210°C or lower, still more preferably 190°C or lower, and particularly preferably 170°C or lower. From the perspective of improving breaking strength, the drying temperature is preferably 10°C or higher, more preferably 100°C or higher, even more preferably 150°C or higher, still more preferably 170°C or higher, still more preferably 190°C or higher, and particularly preferably 210°C or higher. To further improve the strength ratio, it is preferably adjusted appropriately within this temperature range.

[1112] In step (C), the wet powder obtained in step (B) is preferably placed in a container having an air-permeable bottom and / or side surfaces and heat-treated at a temperature of 130°C to 300°C for 2 hours or longer. By performing the heat treatment under such extremely limited conditions, fluorine-containing compounds having a molecular weight of 1000 or less can be efficiently removed together with water, and the contents of the compounds (1) and (2) and the water content can be controlled within the above-mentioned ranges.

[1113] From the perspective of being able to more efficiently remove moisture and fluorine-containing compounds, the temperature of the heat treatment in step (C) is preferably 140°C or higher, more preferably 150°C or higher, further preferably 160°C or higher, further more preferably 180°C or higher, further preferably 200°C or higher, and particularly preferably 220°C or higher. In addition, it is preferably 280°C or lower, more preferably 250°C or lower.

[1114] From the aspect of being able to remove water and fluorine-containing compounds more efficiently, the time of the heat treatment in step (C) is preferably 5 hours or more, more preferably 10 hours or more, and further preferably 15 hours or more. The upper limit is not particularly limited, for example, it is preferably 100 hours, more preferably 50 hours, and further preferably 30 hours.

[1115] From the perspective of more efficiently removing water and fluorinated compounds, the wind speed in step (C) is preferably 0.01 m / s or higher, more preferably 0.03 m / s or higher, even more preferably 0.05 m / s or higher, and even more preferably 0.1 m / s or higher. Furthermore, from the perspective of suppressing powder scattering, the wind speed is preferably 50 m / s or lower, more preferably 30 m / s or lower, and even more preferably 10 m / s or lower.

[1116] The heat treatment in step (C) can be carried out using an electric furnace or a steam furnace. For example, a parallel flow box-type electric furnace, a ventilated box-type electric furnace, a ventilated conveyor-type electric furnace, a belt-type electric furnace, a radiant conveyor-type electric furnace, a fluidized bed electric furnace, a vacuum electric furnace, a stirring electric furnace, an airflow electric furnace, a hot air circulation electric furnace or an electric furnace corresponding to the above (the electric furnace in the device name of each of the above-mentioned electric furnaces is replaced with a device for a steam furnace) can be used for the heat treatment. From the aspect of being able to remove moisture more efficiently, a parallel flow box-type electric furnace, a ventilated box-type electric furnace, a ventilated conveyor-type electric furnace, a belt-type electric furnace, a fluidized bed electric furnace, a hot air circulation electric furnace, and a steam furnace corresponding to the above (the electric furnace in the device name of each of the above-mentioned electric furnaces is replaced with a device for a steam furnace) are preferred.

[1117] From the perspective of more efficiently removing moisture and fluorinated compounds, the heat treatment in step (C) is preferably performed by placing the wet powder in a container with a permeable bottom and / or side surfaces. The container with a permeable bottom and / or side surfaces can be any container capable of withstanding the heat treatment temperature and is preferably made of a metal such as stainless steel.

[1118] The container having an air-permeable bottom and / or side surfaces is preferably a tray (pot) having an air-permeable bottom and / or side surfaces, and more preferably a tray having a mesh bottom and / or side surfaces (mesh tray).

[1119] The mesh is preferably any one of a woven mesh and a punched mesh.

[1120] The mesh size of the net is preferably 2000 μm or less (10 mesh or more according to the ASTM standard), more preferably 595 μm or less (30 mesh or more), further preferably 297 μm or less (50 mesh or more), still more preferably 177 μm or less (80 mesh or more), particularly preferably 149 μm or less (100 mesh or more), and particularly preferably 74 μm or less (200 mesh or more). Furthermore, it is preferably 25 μm or more (500 mesh or less).

[1121] When the net is a woven net, examples of the weaving method include plain weave, twill weave, flat weave, and diagonal weave.

[1122] When the mesh is a punched mesh, the opening ratio is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, and preferably 95% or less.

[1123] In step (C), the amount of the wet powder is preferably 10 g / cm2 in order to more efficiently remove water and fluorine-containing compounds. 2 Below, more preferably 8g / cm 2 Below, more preferably 5g / cm 2 Below, particularly preferably 3 g / cm 2 Below, preferably 0.01 g / cm 2 More preferably, 0.05 g / cm 2 More preferably, 0.1 g / cm 2 above.

[1124] Regarding the moisture content of the wet powder subjected to heat treatment in step (C), from the perspective of being able to more efficiently remove moisture and fluorine-containing compounds, it is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the above-mentioned wet powder. In addition, it is preferably 150% by mass or less, and more preferably 100% by mass or less.

[1125] The TFE-based polymer composition of the present invention is used as a binder for solid-state secondary batteries. The TFE-based polymer composition of the present invention can be used alone in the above-mentioned binder for solid-state secondary batteries, or it can be mixed with other materials (e.g., polymers other than TFE-based polymers). It is preferred that the TFE-based polymer composition of the present invention be used substantially alone, and more preferably alone. It should be noted that the TFE-based polymer composition of the present invention is used substantially alone in a manner such that the amount of the TFE-based polymer composition in the battery binder falls within the range described below.

[1126] The present invention also provides a binder for solid-state secondary batteries (hereinafter also referred to as the binder (1) of the present invention), which is a binder for solid-state secondary batteries that is essentially composed only of a TFE-based polymer co...

Claims

1. A tetrafluoroethylene polymer composition, which is a tetrafluoroethylene polymer composition used as a binder for solid-state secondary batteries, wherein: The composition comprises a tetrafluoroethylene polymer and at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). General formula (1): (H-(CF2) m-1 -COO) p M 1 Wherein, m is 4 to 20, M 1 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, p is 1 or 2, wherein NR 5 R in 4 5 can be the same or different, and are H or an organic group having 1 to 10 carbon atoms, General formula (2): (H-(CF2) n -SO3) q M 2 Where n is 4 to 20, M 2 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, q is 1 or 2, wherein NR 5 R in 4 5 Same as above.

2. A binder for a solid secondary battery, which is a binder for a solid secondary battery consisting essentially of a tetrafluoroethylene polymer composition, wherein: The tetrafluoroethylene polymer composition comprises a tetrafluoroethylene polymer and at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). General formula (1): (H-(CF2) m-1 -COO) p M 1 Wherein, m is 4 to 20, M 1 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, p is 1 or 2, wherein NR 5 R in 4 5 can be the same or different, and are H or an organic group having 1 to 10 carbon atoms, General formula (2): (H-(CF2) n -SO3) q M 2 Where n is 4 to 20, M 2 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, q is 1 or 2, wherein NR 5 R in 4 5 Same as above.

3. The binder for solid-state secondary batteries according to claim 2, wherein In the general formula (1), M 1 is H or NH4, in the general formula (2), M 2 is H or NH4.

4. The binder for solid-state secondary batteries according to claim 2 or 3, wherein The tetrafluoroethylene polymer is polytetrafluoroethylene.

5. The binder for solid-state secondary batteries according to any one of claims 2 to 4, wherein The content of the tetrafluoroethylene polymer is 99.95% by mass or more based on the tetrafluoroethylene polymer composition.

6. The binder for solid-state secondary batteries according to any one of claims 2 to 5, wherein The content of the compound (1) is 1 ppb by mass or more and 1000 ppb by mass or less, and the content of the compound (2) is 5000 ppb by mass or less, relative to the tetrafluoroethylene polymer composition.

7. The binder for solid-state secondary batteries according to any one of claims 2 to 6, wherein The tetrafluoroethylene polymer composition does not substantially contain the compound represented by the following general formula (3): General formula (3): (H-(CF2)8-SO3) q M 2 Where M 2 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, q is 1 or 2, wherein NR 5 R in 4 5 They may be the same or different and are H or an organic group having 1 to 10 carbon atoms.

8. The binder for solid-state secondary batteries according to claim 7, wherein The content of the compound represented by general formula (3) is 25 ppb by mass or less based on the tetrafluoroethylene polymer composition.

9. The binder for solid secondary batteries according to any one of claims 2 to 8, wherein The tetrafluoroethylene polymer composition comprises at least one compound selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (4'), wherein the content of each of the compounds is 1000 ppb by mass or less relative to the tetrafluoroethylene polymer composition. General formula (4): (H-(CF2) 15 -COO) p M 1 Where M 1 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, p is 1 or 2, wherein NR 5 R in 4 5 can be the same or different, and are H or an organic group having 1 to 10 carbon atoms, General formula (4'): (H-(CF2) 16 -COO) p M 1 Where M 1 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, p is 1 or 2, wherein NR 5 R in 4 5 Same as above.

10. The binder for solid-state secondary batteries according to any one of claims 2 to 9, wherein The tetrafluoroethylene polymer composition comprises at least one compound selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'), wherein the content of each of the compounds is 1000 ppb by mass or less relative to the tetrafluoroethylene polymer composition. General formula (5): (H-(CF2) 13 -COO) p M 1 Where M 1 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, p is 1 or 2, wherein NR 5 R in 4 5 can be the same or different, and are H or an organic group having 1 to 10 carbon atoms, General formula (5'): (H-(CF2) 14 -COO) p M 1 Where M 1 H, metal atoms, NR 5 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, p is 1 or 2, wherein NR 5 R in 4 5 Same as above.

11. A tetrafluoroethylene polymer composition used as a binder for a solid secondary battery, the composition being stretchable and having a 0.1% mass loss temperature of 400°C or lower.

12. A tetrafluoroethylene polymer composition used as a binder for a solid secondary battery, the composition being stretchable and having a 1.0% mass loss temperature of 492°C or lower.

13. A tetrafluoroethylene polymer composition used as a binder for a solid-state secondary battery, the composition being stretchable and having a thermal instability index (TII) of 20 or greater.

14. A tetrafluoroethylene polymer composition used as a binder for a solid secondary battery, wherein the composition has a standard specific gravity of 2.200 or less and a 0.1% mass loss temperature of 400°C or less.

15. A tetrafluoroethylene polymer composition used as a binder for a solid secondary battery, wherein the composition has a standard specific gravity of 2.200 or less and a 1.0% mass loss temperature of 492°C or less.

16. The tetrafluoroethylene polymer composition according to claim 15, wherein the standard specific gravity is 2.130 or higher and the 1.0% mass loss temperature is 470°C or higher.

17. The tetrafluoroethylene polymer composition according to claim 15 or 16, wherein The tetrafluoroethylene polymer is polytetrafluoroethylene.

18. The tetrafluoroethylene polymer composition according to any one of claims 15 to 17, wherein The content of the tetrafluoroethylene polymer is 99.95% by mass or more based on the tetrafluoroethylene polymer composition.

19. A mixture for an electrolyte layer, comprising the tetrafluoroethylene polymer composition according to any one of claims 1 and 11 to 18 or the binder for a solid secondary battery according to any one of claims 2 to 10, and a solid electrolyte.

20. The electrolyte layer mixture according to claim 19, wherein The solid electrolyte is a sulfide-based solid electrolyte or an oxide-based solid electrolyte. A solid-state secondary battery comprising the electrolyte layer mixture according to claim 20.

22. An electrode mixture comprising the tetrafluoroethylene polymer composition according to any one of claims 1 and 11 to 18 or the binder for a solid secondary battery according to any one of claims 2 to 10, and an electrode active material.

23. An electrode comprising the polytetrafluoroethylene composition according to any one of claims 1 and 11 to 18 or the binder for a solid secondary battery according to any one of claims 2 to 10, an electrode active material, and a current collector. A solid-state secondary battery comprising the electrode according to claim 23.

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