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

Abstract

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

Description

Technical Field

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

Background Art

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

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

[0004] Patent Documents 2 to 7 describe the use of polytetrafluoroethylene as a binder for a battery.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

[0006] The present disclosure aims to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device capable of obtaining a compound sheet with excellent uniformity, and a binder for an electrochemical device, an electrode compound, an electrode, and a secondary battery using the same. [Means for Solving the Problems]

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

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

[0009] The present disclosure (3) is the tetrafluoroethylene-based polymer composition according to the present disclosure (1) or (2), which is in powder form.

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

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

[0012] The present disclosure (6) is such that the tetrafluoroethylene-based polymer composition contains a tetrafluoroethylene-based polymer. The binder for an electrochemical device according to the present disclosure (5), wherein the tetrafluoroethylene-based polymer is at least one selected from the group consisting of a homopolymer of tetrafluoroethylene and a modified polytetrafluoroethylene containing a polymerization unit based on tetrafluoroethylene and a polymerization unit based on hexafluoropropylene.

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

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

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

[0016] The present disclosure (10) is a binder for an electrochemical device according to the present disclosure (9), wherein the molecular weight of the fluorine-containing compound having a hydrophilic group is 1000 or less.

[0017] The present disclosure (11) is such that the hydrophilic group is -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a, -OCOM a , and -OM a (wherein M a is -H, a metal atom, -NR 1 4, optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, and R 1 is H or an organic group.) is a binder for an electrochemical device according to the present disclosure (9) or (10), selected from the group consisting of at least one.

[0018] In the present disclosure (12), the fluorine-containing compound having the hydrophilic group is represented by the following general formula (N 0 ): X n0 -Rf n0 -Y 0 (N 0 ) (wherein X n0 is H, Cl or F. Rf n0 is an alkylene group having 3 to 20 carbon atoms, linear, branched or cyclic, and in which some or all of the H atoms are substituted by F, and the alkylene group may contain one or more ether bonds and some of the H atoms may be substituted by Cl. Y 0 is an anionic group.) is a binder for an electrochemical device according to any one of the present disclosures (9) to (11).

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

[0020] In the present disclosure (14), the ionic group is -SO3M a , -SO2M a , -PO3M a and -COOM a (wherein M a is -H, a metal atom, -NR 1 4, optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, and R 1is H or an organic group.) and is at least one selected from the group consisting of the binder for an electrochemical device described in the present disclosure (13).

[0021] The present disclosure (15) is the binder for an electrochemical device described in the present disclosure (13) or (14), wherein the content of the ionic group is 0.8 meq / g or more with respect to the polymer compound.

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

[0023] The present disclosure (17) is the binder for an electrochemical device described in any one of the present disclosures (13) to (16), wherein the polymer compound is at least one selected from the group consisting of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II). General formula (I): CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; A 0 is an anionic group; X 2 is H, F, an alkyl group or a fluorine-containing alkyl group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluorine-containing alkyl group; m is an integer of 1 or more.) General formula (II): T X -X A -R FA1 -R FA2 -X A -T X ’ (II) (In the formula, RFA1 is -Rf 1 p -R F -O q - and R FA2 is -Rf 2 p -R FX -O q - and R F is a divalent fluoropolyether group R FX is a divalent fluoropolyether group containing an anionic group Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms p is each independently 0 or 1 q is each independently 0 or 1 X A are each independently a single bond or a divalent to decavalent group T X and T X ’ are each independently (i) a C1 - C 24 (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and does not have the anionic group, and (ii) a C1 - C 24 (hydro)(fluoro)carbon group containing at least one of the anionic groups, and are selected from the group consisting of.)

[0024] The binder for an electrochemical device according to the present disclosure (18) is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a perfluoroether carboxylic acid (III) represented by the following general formula (III), and a polymer containing a polymerization unit (1A) based on a monomer represented by the following general formula (1A) as described in the present disclosure (10) or (11). General formula (1): (H-(CF2) m-1 -COO) p M 1 (wherein m is from 4 to 20. M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF2) n -SO3) q M 2 (wherein n is from 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is the same as above), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.) Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III) (wherein Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is as defined above.) CH2=CF(-CF2-O-Rf-A) (1A) (wherein Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a is -H, a metal atom, -NR 2 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 2 is H or an organic group.).)

[0025] The present disclosure (19) is a binder for an electrochemical device described in any one of the present disclosures (5) to (18) which is in powder form.

[0026] The present disclosure (20) is a binder for an electrochemical device described in any one of the present disclosures (5) to (19), which is a binder for a lithium ion secondary battery.

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

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

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

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

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

[0032] This disclosure (26) is such that the tetrafluoroethylene-based polymer composition contains a tetrafluoroethylene-based polymer, The tetrafluoroethylene-based polymer is at least one selected from the group consisting of a homopolymer of tetrafluoroethylene and a modified polytetrafluoroethylene containing a polymerization unit based on tetrafluoroethylene and a polymerization unit based on hexafluoropropylene, which is the binder for an electrochemical device according to this disclosure (25).

[0033] This disclosure (27) is the binder for an electrochemical device according to this disclosure (25) or (26), which is in powder form.

[0034] This disclosure (28) is the binder for an electrochemical device according to any one of this disclosure (25) to (27), which is a binder for a lithium-ion secondary battery.

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

[0036] This disclosure (30) is the electrode mixture according to this disclosure (29), which is in sheet form.

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

[0038] This disclosure (32) is a secondary battery including the electrode according to this disclosure (31).

Advantages of the Invention

[0039] According to the present disclosure, there can be provided a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device that can obtain a compound sheet excellent in uniformity, and a binder for an electrochemical device, an electrode compound, an electrode, and a secondary battery using the same.

Brief Description of Drawings

[0040]

Figure 1

Embodiments for Carrying Out the Invention

[0041] In the present disclosure, the “organic group” means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. As the above organic group, an alkyl group which may have one or more substituents is preferable.

[0042] Hereinafter, the present disclosure will be specifically described.

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

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

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

[0046] By having the above configuration, the TFE-based polymer compositions of the present disclosure can obtain a uniformly excellent (with little in-plane variation) compounding sheet. Also, a compounding sheet excellent in strength and flexibility can be obtained. In addition, since the TFE-based polymer compositions of the present disclosure can be used dry, it is not necessary to use a large amount of dispersion media such as water and organic solvents, and a wide range of electrode active materials and solid electrolytes to be combined can be selected, which is advantageous in the production process. Also, the processes and costs due to the use of dispersion media can be reduced. Furthermore, since the TFE-based polymer compositions of the present disclosure have excellent adhesion to active materials and electrolytes, the usage amount can be reduced.

[0047] The average particle size of the TFE-based polymer compositions of the present disclosure is 1 μm or more and 300 μm or less. In terms of obtaining a more uniformly excellent compounding sheet, it is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, even more preferably 20 μm or more, even more preferably 30 μm or more. Also, it is preferably 250 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less, even more preferably 100 μm or less, even more preferably 70 μm or less, and even more preferably 50 μm or less. The above average particle size is determined by the following laser diffraction method. Using a HELOS&RODOS system (trade name, manufactured by SYMPATEC), it is carried out dry. The powder to be measured dispersed by compressed air with a dispersion pressure of 2 bar is measured by the measurement sensor detecting the shadow of the powder to be measured projected by the laser, and the particle size distribution of the powder to be measured is calculated, and the value of the average particle size (50% integrated particle size) D50 on a volume basis is obtained. D50 is assumed to be equal to the particle size corresponding to 50% of the integrated particle size distribution.

[0048] The TFE-based polymer composition (1) of the present disclosure has an average aspect ratio of 2.0 or less. The TFE-based polymer composition (2) of the present disclosure preferably has an average aspect ratio of 2.0 or less. In terms of obtaining a compound sheet with even better uniformity, the above average aspect ratio is preferably 1.9 or less, more preferably 1.8 or less, still more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, still more preferably 1.4 or less, still more preferably 1.3 or less, still more preferably 1.2 or less, particularly preferably 1.1 or less. The above average aspect ratio may also be 1.0 or more. The above average aspect ratio is determined by observing the TFE-based polymer composition with a scanning electron microscope (SEM), performing image processing on 200 or more randomly extracted particles, and calculating the average of the ratios of the major axis to the minor axis.

[0049] The TFE-based polymer composition (1) of the present disclosure preferably has a proportion of particles with an aspect ratio of 3.0 or more of 15% or less. The TFE-based polymer composition (2) of the present disclosure has a proportion of particles with an aspect ratio of 3.0 or more of 15% or less. In terms of obtaining a compound sheet with even better uniformity, the proportion of particles with an aspect ratio of 3.0 or more is preferably 13% or less, more preferably 10% or less, still more preferably 8% or less, still more preferably 5% or less, particularly preferably less than 5%. The above proportion may also be 1% or more. The above proportion is determined by observing the TFE-based polymer composition with a scanning electron microscope (SEM), performing image processing on 200 or more randomly extracted particles, calculating the aspect ratio of each particle from the ratio of the major axis to the minor axis, and obtaining the proportion relative to the total number of the above extracted particles.

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

[0051] The TFE-based polymer composition of the present disclosure is preferably non-melt processable. In this specification, being non-melt processable means that the melt flow rate (MFR) is less than 0.25 g / 10 min, preferably less than 0.10 g / 10 min, more preferably 0.05 g / 10 min or less, still more preferably 0.01 g / 10 min or less. The above MFR is a value obtained as the mass (g / 10 min) of the polymer flowing out per 10 minutes from a nozzle with an inner diameter of 2.095 mm and a length of 8 mm at 372 °C and a load of 5 kg using a melt indexer in accordance with ASTM D1238.

[0052] The TFE-based polymer composition of the present disclosure contains a TFE-based polymer. The above TFE-based polymer may be a homopolymer of TFE, or may be a TFE copolymer containing a polymerization unit based on TFE (TFE unit) and a polymerization unit based on a modified monomer copolymerizable with TFE (modified monomer unit). The above TFE-based polymer may be polytetrafluoroethylene (PTFE). The above PTFE includes a homopolymer of TFE and a modified PTFE containing 99.0 mass% or more of TFE units and 1.0 mass% or less of modified monomer units. The above TFE-based polymer is preferably PTFE and more preferably modified PTFE in that a compounding sheet with even better uniformity, strength and flexibility can be obtained. In the present disclosure, the homopolymer of TFE refers to a polymer in which the content of the modified monomer unit is less than 0.0001% by mass based on all the polymerization units.

[0053] The content of the modified monomer unit is preferably in the range of 0.0001 to 10% by mass based on all the polymerization units in terms of obtaining a composite sheet having better uniformity, strength, and flexibility. As the lower limit of the content of the modified monomer unit, 0.001% by mass is more preferable, 0.010% by mass is further preferable, 0.015% by mass is even more preferable, and 0.020% by mass is particularly preferable. As the upper limit of the content of the modified monomer unit, 5.0% by mass is preferable, 3.0% by mass is more preferable, 1.0% by mass is further preferable, 0.80% by mass is even more preferable, 0.60% by mass is even more preferable, 0.50% by mass is even more preferable, 0.40% by mass is even more preferable, 0.30% by mass is even more preferable, 0.20% by mass is even more preferable, and 0.10% by mass is particularly preferable. In this specification, the above-mentioned modified monomer unit means a part of the molecular structure of the TFE-based polymer and is a part derived from the modified monomer.

[0054] The content of each of the above-mentioned polymerization units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

[0055] The above-mentioned modified monomer is not particularly limited as long as it can copolymerize with TFE. For example, perfluoroolefins such as hexafluoropropylene [HFP]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as chlorotrifluoroethylene [CTFE]; perfluorovinyl ether; perfluoroallyl ether; (perfluoroalkyl)ethylene, ethylene, monomers having a polar group, etc. can be mentioned. Further, the modified monomer used may be one type or a plurality of types.

[0056] The above-mentioned perfluorovinyl ether is not particularly limited. For example, the following general formula (A): CF2=CF-ORf 1 (A) (wherein, Rf 1 represents a perfluoro organic group.) Examples thereof include perfluoro unsaturated compounds represented by the formula. In the present specification, the above-mentioned "perfluoro organic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen.

[0057] Examples of the above-mentioned perfluorovinyl ether include, for example, in the above general formula (A), Rf 1 is a perfluoro(alkyl vinyl ether) [PAVE] in which the perfluoroalkyl group has 1 to 10 carbon atoms. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

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

[0059] Examples of the above-mentioned perfluorovinyl ether further include, in the above general formula (A), those in which Rf 1 is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf 1 is a group represented by the following formula:

[0060]

Chemical formula

[0061] (wherein, m represents an integer of 0 or 1 to 4), and those in which Rf 1 is a group represented by the following formula:

[0062]

Chemical formula

[0063] Groups represented by (wherein n represents an integer of 1 to 4) etc. may be mentioned.

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

[0065] Examples of the perfluoroallyl ether include the general formula (B): CF2=CF-CF2-ORf 2 (B) (wherein Rf 2 represents a perfluoro organic group.) Fluoromonomers represented by may be mentioned.

[0066] The above Rf 2 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms. As the above perfluoroallyl ether, at least one selected from the group consisting of CF2=CF-CF2-O-CF3, CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is preferable, at least one selected from the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is more preferable, and CF2=CF-CF2-O-CF2CF2CF3 is still more preferable.

[0067] The above modified monomer is represented by the following general formula (i): CX 1 X 2 =CX 3 X 4 (i) (wherein X 1 ~X 3 are each independently H or F. X 4 is F, Cl, Rf or O-Rf. Rf is a perfluoro organic group.) It is preferably a compound represented by.

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

[0069] The monomer having the polar group may be a non-fluorine monomer or a fluorine-containing monomer.

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

[0071] The monomer having the polar group preferably includes a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group (hereinafter referred to as "modified monomer (A)").

[0072] Examples of the hydrophilic group in the modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, and may be the same or different. Any two of them may be bonded to each other to form a ring.). Among them, as the hydrophilic group, -SO3M or -COOM is preferable. R 7 is preferably H or an organic group of C 1-10 and more preferably H or an organic group of C 1-4 and still more preferably H or an alkyl group of C 1-4 . Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferable.

[0073] Examples of the "functional group capable of reacting by radical polymerization" in the modified monomer (A) include groups having an ethylenically unsaturated bond such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond has the following formula: CX e X g =CX f R- (wherein X e , X f and X g are each independently F, Cl, H, CF3, CF2H, CFH2, or CH3; and R is a linking group.). Examples of the linking group of R include the linking group as R a described later. Preferably, -CH=CH2, -CF=CH 2、 -CH=CF 2、Groups having unsaturated bonds such as -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CH=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, -O-CF2-CF=CF2, etc. are included.

[0074] Since the above-mentioned modified monomer (A) has a functional group capable of reacting by radical polymerization, when used in polymerization, it is presumed to react with the fluorine-containing monomer at the initial stage of the polymerization reaction to form particles having a hydrophilic group derived from the above-mentioned modified monomer (A) and high stability. Therefore, when polymerization is carried out in the presence of the above-mentioned modified monomer (A), the number of particles is considered to increase.

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

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

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

[0078] In the above formula (4a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. Y 3 is preferably -COOM 1 in terms of obtaining appropriate water solubility and surface activity, and M 1 is preferably H or NH4 in terms of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body.

[0079] Examples of the perfluorovinyl alkyl compound represented by the above formula (4a) include, for example, CF2=CFCF2COOM 1 (wherein, M 1 is the same as defined above.)

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

[0081] In the above formula (4c), n3 is preferably an integer of 5 or less in terms of water solubility, and Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and surface activity 1 and M 1 is preferably H or NH4 in that the dispersion stability is improved

[0082] In the above formula (4d), X 1 is preferably -CF3 in terms of surface activity, n4 is preferably an integer of 5 or less in terms of water solubility, and Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and surface activity 1 and M 1 is preferably H or NH4

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

[0084] In the above formula (4e), n5 is preferably 0 or an integer of 1 to 5 in terms of emulsifying ability, more preferably 0, 1 or 2, and still more preferably 0 or 1. Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and surface activity 1 and M 1 is preferably H or NH4 in that it is difficult to remain as an impurity and the heat resistance of the obtained molded article is improved

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

[0086] As the above-mentioned modified monomer, at least one selected from the group consisting of HFP, PAVE, PFAE, and a monomer having a polar group is preferable in terms of improving stretchability, adhesiveness, and flexibility of the binder sheet. More preferably, at least one selected from the group consisting of HFP, perfluoro(methyl vinyl ether) [PMVE], perfluoro(propyl vinyl ether) [PPVE], PFBE, a non-fluorine monomer having an acid anhydride residue, and the modified monomer (A) is more preferable. Even more preferably, at least one selected from the group consisting of HFP, PMVE, PPVE, a cyclic non-fluorine monomer having an acid anhydride residue, and a compound represented by the general formula (4e) is even more preferable. Even more preferably, at least one selected from the group consisting of HFP and PPVE is even more preferable, and HFP is even more preferable.

[0087] The above-mentioned TFE-based polymer may have a core-shell structure. Examples of the TFE-based polymer having a core-shell structure include modified PTFE containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE in the particles. Examples of such modified PTFE include PTFE described in Japanese Patent Application Laid-Open No. 2005-527652.

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

[0089] The content of the TFE-based polymer in the TFE-based polymer composition of the present disclosure may be 95.0% by mass or more, preferably 98.0% by mass or more, more preferably 99.0% by mass or more, still more preferably 99.5% by mass or more, particularly preferably 99.9% by mass or more, and most preferably 99.95% by mass or more, based on the TFE-based polymer composition.

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

[0091] Examples of the hydrophilic group include -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a , -OCOM a , and -OM a (wherein M a is -H, a metal atom, -NR 1 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and R 1 is H or an organic group). At least one selected from the group consisting of these is included. The hydrophilic group may be an ionic group, and is preferably an anionic group.

[0092] Examples of the fluorine-containing compound having a hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 g / mol or less. The molecular weight of the fluorine-containing compound is preferably 800 or less, and more preferably 500 or less. It is normal that the polymer particles obtained by polymerization carried out in the presence of a fluorine-containing surfactant contain, in addition to the TFE-based polymer, the fluorine-containing surfactant. In the present specification, the fluorine-containing surfactant is one used during polymerization. The fluorine-containing compound with a molecular weight of 1000 or less may be a compound that is not added during polymerization, for example, a compound that is by-produced during the polymerization process. In addition, when the fluorine-containing compound with a molecular weight of 1000 or less contains an anionic part and a cationic part, it means a fluorine-containing compound in which the molecular weight of the anionic part is 1000 or less. The TFE-based polymer shall not be included in the fluorine-containing compound with a molecular weight of 1000 or less.

[0093] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include surfactants containing fluorine in which the molecular weight of the anionic part is 1000 or less (anionic fluorine-containing surfactants). The above-mentioned "anionic part" means the part excluding the cation of the above-mentioned fluorine-containing surfactant. For example, in the case of F(CF2) n1 COOM, it is the part of "F(CF2) n1 COO".

[0094] Examples of the above-mentioned anionic fluorine-containing surfactant include the general formula (N 0 ): X n0 -Rf n0 -Y 0 (N 0 ) (In the formula, X n0 is H, Cl or F. Rf n0 is an alkylene group having 3 to 20 carbon atoms, which is linear, branched or cyclic, and in which some or all of the H are substituted by F, and the alkylene group may contain one or more ether bonds, and some of the H may be substituted by Cl. Y 0 is an anionic group.) Compounds represented by the formula are included.

[0095] The anionic group of Y 0 may be -COOM, -SO2M, or -SO3M, and may be -COOM or -SO3M. M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 7is H or an organic group. Examples of the above metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li. R 7 may be H or a C 1-10 organic group, may be H or a C 1-4 organic group, may be H or a C 1-4 alkyl group. M may be H, a metal atom, or NR 7 4, may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 7 4, may be H, Na, K, Li, or NH4. The above Rf n0 may be one in which 50% or more of H is substituted with fluorine.

[0096] Examples of the compound represented by the general formula (N 0 ) include those represented by the general formula (N 1 ): X n0 -(CF2) m1 -Y 0 (N 1 ) (In the formula, X n0 is H, Cl, or F, m1 is an integer from 3 to 15, and Y 0 is as defined above.) Compounds represented by the formula, general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 ) (In the formula, Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer from 0 to 3, X n1 is F or CF3, and Y 0 is as defined above.) Compounds represented by the formula, general formula (N 3 ): Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 ) (wherein, Rf n2 is a partially or fully fluorinated alkyl group which may contain an ether bond having 1 to 13 carbon atoms, m3 is an integer of 1 to 3, and Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y 0 is as defined above.) A compound represented by the general formula (N 4 ): Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 ) (wherein, Rf n4 is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond having 1 to 12 carbon atoms and / or a chlorine atom, Y n1 and Y n2 are the same or different and are H or F, p is 0 or 1, and Y 0 is as defined above.) A compound represented by the general formula (N 5 ): [Chemical formula] (wherein, X n2 , X n3 and X n4 may be the same or different and are H, F, or a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond having 1 to 6 carbon atoms. Rf n5 is a linear or branched partially or fully fluorinated alkylene group which may contain an ether bond having 1 to 3 carbon atoms, L is a linking group, and Y 0 is as defined above. However, the total number of carbon atoms of X n2 , X n3 , X n4 and Rf n5 is 18 or less.) Examples thereof include compounds represented by the formula.

[0097] General formula (N 0More specifically, examples of the compound represented by ()) include perfluorocarboxylic acid (I) represented by general formula (I), ω-H perfluorocarboxylic acid (II) represented by general formula (II), perfluoroether carboxylic acid (III) represented by general formula (III), perfluoroalkyl alkylene carboxylic acid (IV) represented by general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by general formula (V), perfluoroalkylsulfonic acid (VI) represented by general formula (VI), ω-H perfluorosulfonic acid (VII) represented by general formula (VII), perfluoroalkyl alkylene sulfonic acid (VIII) represented by general formula (VIII), alkyl alkylene carboxylic acid (IX) represented by general formula (IX), fluorocarboxylic acid (X) represented by general formula (X), alkoxyfluorosulfonic acid (XI) represented by general formula (XI), compound (XII) represented by general formula (XII), compound (XIII) represented by the following general formula (XIII), and the like.

[0098] The above perfluorocarboxylic acid (I) has the general formula (I): F(CF2) n1 COOM (I) (In the formula, n1 is an integer from 3 to 14, and M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 7 is H or an organic group.)

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

[0100] The above perfluoroether carboxylic acid (III) has the general formula (III): Rf 1 -O-(CF(CF3)CF2O) n3CF(CF3)COOM (III) (wherein, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.) is represented by the formula.

[0101] The above perfluoroalkylalkylene carboxylic acid (IV) has the general formula (IV): Rf 2 (CH2) n4 Rf 3 COOM (IV) (wherein, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above.) is represented by the formula.

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

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

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

[0105] The above perfluoroalkylalkylene sulfonic acid (VIII) is represented by the general formula (VIII): Rf 5 (CH2) n7 SO3M (VIII) (wherein Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer from 1 to 3, and M is as defined above.)

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

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

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

[0109] The above compound (XII) has the general formula (XII):

Chemical formula

[0110] The above compound (XIII) has the following general formula (XIII): Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM (XIII) (wherein, Rf 11 is a fluoroalkyl group having 1 to 5 carbon atoms which contains chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above.) is represented thereby. Examples of compound (XIII) include CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10CF2COONH4 (a mixture with an average molecular weight of 750, where n9 and n10 are as defined above.) can be mentioned.

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

[0112] The fluorine-containing surfactant may be a single fluorine-containing surfactant or a mixture containing two or more fluorine-containing surfactants.

[0113] Examples of the fluorine-containing surfactant include compounds represented by the following formulas. The fluorine-containing surfactant may be a mixture of these compounds. F(CF2)7COOM, F(CF2)5COOM, H(CF2)6COOM, H(CF2)7COOM, CF3O(CF2)3OCHFCF2COOM, C3F7OCF(CF3)CF2OCF(CF3)COOM, CF3CF2CF2OCF(CF3)COOM, CF3CF2OCF2CF2OCF2COOM, C2F5OCF(CF3)CF2OCF(CF3)COOM, CF3OCF(CF3)CF2OCF(CF3)COOM, CF2ClCF2CF2OCF(CF3)CF2OCF2COOM, CF2ClCF2CF2OCF2CF(CF3)OCF2COOM, CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM, CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, and, [Chemical formula] (In each formula, M is H, a metal atom, NR 74. It is imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent. R 7 is H or an organic group.).

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

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

[0116] The amount of the anionic fluorine-containing surfactant is measured by the following method. Weigh 1 g of the sample, add 10 g (12.6 ml) of methanol, perform ultrasonic treatment for 60 minutes to obtain an extract. Appropriately concentrate the obtained extract by nitrogen purging, and measure the fluorine-containing compound in the concentrated extract by LC / MS / MS. Extract the molecular weight information from the obtained LC / MS spectrum and confirm the match with the structural formula of the candidate fluorine-containing compound. Prepare aqueous solutions with a content of 5 levels or more of the standard substance, perform LC / MS analysis on the aqueous solutions with each content, plot the relationship between the content and the area of the peak corresponding to that content, and draw a calibration curve. Using the above calibration curve, convert the area of the peak in the LC / MS chromatogram of the fluorine-containing compound in the extract into the content of the fluorine-containing compound. Note that the lower limit of quantification in this measurement method is 10 mass ppb.

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

[0118] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include a compound represented by the following general formula (1) (hereinafter also referred to as compound (1)). General formula (1): (H-(CF2) m-1 -COO) p M 1 (In the formula, m is 4 to 20. M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) M 1 is preferably H.

[0119] M 1 Examples of the metal atom as M include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. The four Rs5 may be the same or different. R 5 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

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

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

[0122] The content of compound (1) (when two or more are present, the content for each component) may be 10 mass ppm or less, preferably 5000 mass ppb or less, more preferably 1000 mass ppb or less, still more preferably 500 mass ppb or less, still more preferably 100 mass ppb or less, still more preferably 50 mass ppb or less, still more preferably 25 mass ppb or less, and particularly preferably 10 mass ppb or less with respect to the above TFE-based polymer. The lower limit is not particularly limited, but may be 0.1 mass ppb or may be 1 mass ppb.

[0123] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include a compound represented by the following general formula (2) (hereinafter also referred to as compound (2)). General formula (2): (H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is the same as above), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.) M 2 As for this, H is preferable.

[0124] M 2 Examples of the metal atom as M include monovalent and divalent metal atoms, and examples thereof include alkali metals (Group 1) and alkaline earth metals (Group 2), and specifically, Na, K, Li and the like are exemplified. Four Rs 5 may be the same or different. R 5 is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms.

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

[0126] The TFE-based polymer composition of the present disclosure may contain one or more of Compound (2), or may contain two or more thereof, or may contain three or more thereof.

[0127] The content of Compound (2) (when two or more are present, the content for each component) may be 10 mass ppm or less with respect to the above TFE-based polymer, preferably 5000 mass ppb or less, more preferably 1000 mass ppb or less, still more preferably 500 mass ppb or less, still more preferably 100 mass ppb or less, still more preferably 50 mass ppb or less, still more preferably 25 mass ppb or less, still more preferably 10 mass ppb or less, still more preferably 1 mass ppb or less, still more preferably less than 1 mass ppb, and particularly preferably less than the lower limit of quantification. The lower limit is not particularly limited and may be an amount less than the lower limit of quantification.

[0128] The TFE-based polymer composition containing compound (1) and / or (2) is obtained by using a hydrocarbon surfactant. The TFE-based polymer composition of the present disclosure may contain a hydrocarbon surfactant together with a TFE-based polymer and compound (1) and / or (2). The content of the hydrocarbon surfactant in the above TFE-based polymer composition is not particularly limited, but is usually 100 mass ppm to 10 mass%. It is preferable that the proportion of hydrogen atoms bonded to carbon atoms in the above hydrocarbon surfactant that are substituted with fluorine atoms is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0129] The TFE-based polymer composition of the present disclosure preferably does not substantially contain a compound represented by the following general formula (3) (hereinafter also referred to as compound (3)). General formula (3): (H-(CF2)8-SO3) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group having 1 to 10 carbon atoms (preferably an organic group not containing fluorine), an imidazolium that may have a substituent, a pyridinium that may have a substituent, or a phosphonium that may have a substituent. q is 1 or 2.)

[0130] Not substantially containing compound (3) means that the content of compound (3) is 25 mass ppb or less with respect to the above TFE-based polymer. The content of compound (3) is preferably 20 mass ppb or less, more preferably 15 mass ppb or less, still more preferably 10 mass ppb or less with respect to the above TFE-based polymer. The lower limit is not particularly limited, and may be 0 mass ppb, 0.1 mass ppb, or 1 mass ppb.

[0131] The contents of the compounds (1), (2), and (3) are the values measured using liquid chromatography mass spectrometry as described in the examples described later.

[0132] Examples of the fluorine-containing compound having the hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000 g / mol.

[0133] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000 include, for example, a polymer compound having an ionic group. Note that the above TFE-based polymer is not included in the above polymer compound.

[0134] As the ionic group, an anionic group is preferable, and examples thereof include a sulfate group, -COOM a (carboxylate group), a phosphate group, -PO3M a (phosphonate group), -SO3M a (sulfonate group), -SO2M a (sulfinate group), -C(CF3)2OM a (In each formula, M a is -H, a metal atom, -NR 2 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 2 is H or an organic group.) and the like. Among them, at least one selected from the group consisting of -SO3M a , -SO2M a , -PO3M a and -COOM a is preferable, and -COOM a is more preferable.

[0135] The content of the ionic group is preferably 0.80 meq / g or more, more preferably 1.20 meq / g or more, still more preferably 1.75 meq / g or more, even more preferably 2.00 meq / g or more, and particularly preferably 2.50 meq / g or more, based on the above polymer compound. The content may also be 10.0 meq / g or less, 8.00 meq / g or less, or 5.00 meq / g or less. The content of the ionic group is determined by calculation from the composition of the above polymer compound.

[0136] The above polymer compound preferably contains fluorine atoms, and preferably, the ratio of hydrogen atoms bonded to carbon atoms in the polymer compound replaced by fluorine atoms is 50% or more. The "ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms" is determined as the ratio of the number of fluorine atoms to the total number of hydrogen atoms bonded to carbon atoms and halogen atoms (including fluorine atoms) bonded to carbon atoms. The ratio of hydrogen atoms bonded to carbon atoms replaced by fluorine atoms in the above polymer compound is not particularly limited, but is more preferably 70% or more, still more preferably 80% or more, even more preferably 90% or more, particularly preferably 95% or more, and most preferably 100%.

[0137] The above polymer compound preferably has an ion exchange ratio (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the main chain of the polymer compound relative to the ionic group. A precursor group that becomes ionic by hydrolysis (for example, -SO2F) is not regarded as an ionic group for the purpose of determining the IXR. The above IXR is preferably 0.5 or more, more preferably 1 or more, still more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. Also, the IXR is preferably 43 or less, more preferably 33 or less, and still more preferably 23 or less. In the above-mentioned polymer compound, the ionic groups are typically distributed along the polymer main chain. The above-mentioned polymer compound includes repeating side chains bonded to the polymer main chain, and it is preferable that these side chains have ionic groups.

[0138] The above-mentioned polymer compound is preferably a water-soluble polymer compound. "Water-soluble" means the property of being easily dissolved or dispersed in an aqueous medium. A polymer compound having water solubility can, for example, have its particle diameter unable to be measured by the dynamic light scattering method (DLS), or show a particle diameter of 5 nm or less. On the other hand, a polymer compound having water insolubility can, for example, have its particle diameter measured to be more than 5 nm by the dynamic light scattering method (DLS).

[0139] As for the number average molecular weight of the above-mentioned polymer compound, more than 0.1×10 4 is preferable, more than 0.15×10 4 is more preferable, more than 0.2×10 4 is still more preferable, more than 0.3×10 4 is even more preferable, more than 0.5×10 4 is even more preferable, more than 1.0×10 4 is particularly more preferable, more than 2.0×10 4 is particularly preferable, more than 3.0×10 4 is most preferable. Also, less than 75.0×10 4 is preferable, less than 50.0×10 4 is more preferable, less than 40.0×10 4 is still more preferable, less than 30.0×10 4 is particularly more preferable, less than 20.0×10 4 is particularly preferable.

[0140] As for the weight average molecular weight of the above-mentioned polymer compound, more than 0.1×10 4 is preferable, more than 0.2×10 4 is more preferable, more than 0.4×10 4 is still more preferable, more than 0.6×10 4 is even more preferable, more than 1.0×10 4 is even more preferable, more than 2.0×10 4The above is particularly preferred, 5.0×10 4 The above is most preferred. Also, 150.0×10 4 The following is preferred, 100.0×10 4 The following is more preferred, 80.0×10 4 The following is still more preferred, 60.0×10 4 The following is even more preferred, 40.0×10 4 The following is particularly preferred.

[0141] The above number average molecular weight and weight average molecular weight are values calculated by gel permeation chromatography (GPC) using monodisperse polystyrene, or monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) as standards for molecular weight. Also, when measurement by GPC is not possible, the number average molecular weight of the above polymer compound can be determined from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0142] The above polymer compound preferably does not substantially contain a fraction having a molecular weight of 1000 or less, more preferably does not substantially contain a fraction having a molecular weight of less than 1500, still more preferably does not substantially contain a fraction having a molecular weight of less than 2000, and particularly preferably does not substantially contain a fraction having a molecular weight of less than 3000. Not substantially containing the above fraction means that the content of the above fraction in the above polymer compound is 3.0% by mass or less. The content of the above fraction is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less with respect to the above polymer compound. The content of the above fraction can be measured by gel permeation chromatography (GPC) or liquid chromatography - mass spectrometry (LC - MS).

[0143] The above polymer compound preferably substantially does not contain a fluorine-containing compound having a molecular weight of 1000 or less. Substantially not containing the fluorine-containing compound means that the amount of the fluorine-containing compound is 25 mass ppb or less with respect to the polymer compound. The amount of the fluorine-containing compound is more preferably less than 25 mass ppb, still more preferably 10 mass ppb or less, still more preferably less than 10 mass ppb, still more preferably 5 mass ppb or less, still more preferably 3 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably less than 1 mass ppb. The lower limit is not particularly limited and may be an amount less than the detection limit. The fluorine-containing compound having a molecular weight of 1000 or less and its quantification method will be described later.

[0144] The above polymer compound is preferably at least one selected from the group consisting of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II). General formula (I): CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; A 0 is an anionic group; X 2 is H, F, an alkyl group or a fluorine-containing alkyl group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluorine-containing alkyl group; m is an integer of 1 or more.) General formula (II): T X -X A -R FA1 -R FA2 -X A -T X’ (II) (wherein R FA1 is -Rf 1 p -R F -O q -; and R FA2 is -Rf 2 p -R FX -O q -; and R F is a divalent fluoropolyether group; R FX is a divalent fluoropolyether group containing an anionic group; Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms; p is each independently 0 or 1; q is each independently 0 or 1; X A are each independently a single bond or a divalent to decavalent group; T X and T X ’ are each independently (i) a C1-C 24 (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and does not have the above anionic group, and (ii) a C1-C 24 (hydro)(fluoro)carbon group containing at least one of the above anionic groups, selected from the group consisting of.)

[0145] Polymer (I) is a polymer containing a polymerization unit (I) based on monomer (I). Monomer (I) is represented by the following general formula (I). CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (wherein X 1 and X 3is independently F, Cl, H, or CF3; X 2 is H, F, an alkyl group, or a fluorinated alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more.) X 2 is preferably F, Cl, H, or CF3. Also, Z 1 and Z 2 are preferably F or CF3.

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

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

[0148] R is a linking group. In the present disclosure, the "linking group" is an (m + 1)-valent linking group, and when m is 1, it is a divalent linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. The upper limit is not limited, but for example, it may be 100 or less, or 50 or less.

[0149] The linking group may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and may optionally contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may optionally contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate. The above linking group may not contain a carbon atom and may be a chain heteroatom such as oxygen, sulfur, or nitrogen.

[0150] m is an integer of 1 or more, preferably 1 or 2, more preferably 1. When m is an integer of 2 or more, Z 1 , Z 2 and A 0 may be the same or different. Next, a preferred configuration when m is 1 in the general formula (I) will be described.

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

[0152] The polymer (I) is also preferably highly fluorinated. For example, excluding anionic groups (A a ) such as phosphate group moieties (e.g., CH2OP(O)(OM a )2) and sulfate group moieties (e.g., CH2OS(O)2OM 0 ), it is preferred that 80% or more, 90% or more, 95% or more, or 100% of the C-H bonds in the polymer (I) are replaced by C-F bonds.

[0153] The monomer (I) and the polymer (I) preferably have C-F bonds and no C-H bonds except for the anionic group (A 0 ). That is, in the general formula (I), X 1 , X 2 , and X 3All of them are F, and R is preferably a perfluoroalkylene group having 1 or more carbon atoms. The above perfluoroalkylene group may be either linear or branched, and may be either cyclic or acyclic, and may contain at least one catenary heteroatom. The number of carbon atoms of the above perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0154] The monomer (I) and the polymer (I) may be partially fluorinated. That is, the monomer (I) and the polymer (I) preferably have at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom, except for the anionic group (A 0 ).

[0155] The anionic group (A 0 ) is -SO3M a , -OSO3M a , -SO2M a , -COOM a , -SO2NR’CH2COOM a , -CH2OP(O)(OM a )2, [-CH2O]2P(O)(OM a ), -CH2CH2OP(O)(OM a )2, [-CH2CH2O]2P(O)(OM a ), -CH2CH2OSO3M a , -P(O)(OM a )2, -SO2NR’CH2CH2OP(O)(OM a )2, [-SO2NR’CH2CH2O]2P(O)(OM a ), -CH2OSO3M a , -SO2NR’CH2CH2OSO3M a , or -C(CF3)2OM a . Among them, -SO3M a , -OSO3M a , -COOM a , -P(O)(OM a )2 or C(CF3)2OM a is preferable, and -COOM a , -SO3M a, -OSO3M a or C(CF3)2OM a is more preferred, -SO3M a , -COOM a or P(O)(OM a )2 is even more preferred, -SO3M a or COOM a is particularly preferred, -COOM a is most preferred.

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

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

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

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

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

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

[0162] In the general formula (I), A 0 is preferably one form that is a sulfate group. A 0 is, for example, -CH2OSO3M a , -CH2CH2OSO3M a , or -SO2NR’CH2CH2OSO3M a , where R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.)

[0163] A 0 When A a is a sulfate group, examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2CH2OSO3M a ), CH2=CH(O(CF2)4CH2OSO3M a ), CF2=CF(O(CF2)4CH2OSO3M a ), CF2=CF(OCF2CF(CF3)CH2OSO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M a)、CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M a )、CH2=CH(OCF2CF2CH2OSO3M a )、CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M a )、CH2=CH(OCF2CF2CF2CH2OSO3M a ) etc. are mentioned. In the above formula, M a is the same as above.

[0164] In general formula (I), A 0 being a sulfonate group is also one of the preferred forms. As A 0 , for example, it is -SO3M a , and in the formula, M a is the same as above.

[0165] When A 0 is a sulfonate group, examples of the monomer represented by general formula (I) include CF2=CF(OCF2CF2SO3M a ), CF2=CF(O(CF2)3SO3M a ), CF2=CF(O(CF2)4SO3M a ), CF2=CF(OCF2CF(CF3)SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M a ), CH2=CH(OCF2CF2SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M a ), CH2=CH(O(CF2)4SO3M a ), CH2=CH(O(CF2)3SO3M a ) etc. are mentioned. In the above formula, M a is the same as above.

[0166] In general formula (I), A 0 being a sulfinate group is also one of the preferred forms. As A 0 , for example, it is -SO2M a , and in the formula, M a is the same as above.

[0167] A 0 is a sulfinate group, and examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2SO2M a ), CF2=CF(O(CF2)3SO2M a ), CF2=CF(O(CF2)4SO2M a ), CF2=CF(OCF2CF(CF3)SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO2M a ), CH2=CH(OCF2CF2SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2M a ), CH2=CH(O(CF2)4SO2M a ), CH2=CH(O(CF2)3SO2M a ), etc. In the above formula, M a is the same as above.

[0168] In the general formula (I), it is also a preferred form that A 0 is a carboxylate group. Examples of A 0 include, for example, COOM a or SO2NR’CH2COOM a , where R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above. When A 0 is a carboxylate group, examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2COOM a ), CF2=CF(O(CF2)3COOM a ), CF2=CF(O(CF2)4COOM a ), CF2=CF(O(CF2)5COOM a ), CF2=CF(OCF2CF(CF3)COOM a ), CF2=CF(OCF2CF(CF3)O(CF2) n COOM a )(n is greater than 1), CH2=CH(OCF2CF2COOM a ), CH2=CH(O(CF2)4COOMa )、CH2=CH(O(CF2)3COOM a )、CF2=CF(OCF2CF2SO2NR’CH2COOM a )、CF2=CF(O(CF2)4SO2NR’CH2COOM a )、CF2=CF(OCF2CF(CF3)SO2NR’CH2COOM a )、CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM a )、CH2=CH(OCF2CF2SO2NR’CH2COOM a )、CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM a )、CH2=CH(O(CF2)4SO2NR’CH2COOM a )、CH2=CH(O(CF2)3SO2NR’CH2COOM a ) etc. may be mentioned. In the above formula, R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0169] In general formula (I), A 0 being a phosphate group is also one of the preferred forms. A 0 includes, for example, -CH2OP(O)(OM a )2, [-CH2O]2P(O)(OM a ), -CH2CH2OP(O)(OM a )2, [-CH2CH2O]2P(O)(OM a ), [-SO2NR’CH2CH2O]2P(O)(OM a ) or SO2NR’CH2CH2OP(O)(OM a )2, where R’ is an alkyl group having 1 to 4 carbon atoms and M a is the same as above.

[0170] A 0 being phosphate, the monomer represented by general formula (I) includes CF2=CF(OCF2CF2CH2OP(O)(OM a )2), CF2=CF(O(CF2)4CH2OP(O)(OM a)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CH2=CH(OCF2CF2CH2OP(O)(OM a )2), CH2=CH(O(CF2)4CH2OP(O)(OM a )2), CH2=CH(O(CF2)3CH2OP(O)(OM a )2), etc. In the above formula, M a is the same as above.

[0171] In general formula (I), it is also a preferred form that A 0 is a phosphonate group. When A 0 is a phosphonate group, examples of the monomer represented by general formula (I) include CF2=CF(OCF2CF2P(O)(OM a )2), CF2=CF(O(CF2)4P(O)(OM a )2), CF2=CF(OCF2CF(CF3)P(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM a )2), CH2=CH(OCF2CF2P(O)(OM a )2), CH2=CH(O(CF2)4P(O)(OM a )2), CH2=CH(O(CF2)3P(O)(OM a )2). In the formula, M a is the same as above.

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

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

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

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

[0176] In general formula (1), Y is -H, -F, an alkyl group, or a fluorinated alkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above fluorinated alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above Y, -H, -F, or CF3 is preferable, and -F is more preferable.

[0177] In general formula (1), Z is the same or different and is -H, -F, an alkyl group, or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above fluorinated alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above Z, -H, -F, or CF3 is preferable, and -F is more preferable.

[0178] In general formula (1), at least one of X, Y, and Z contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

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

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

[0181] The number of carbon atoms of the fluorine-containing alkylene group having the above-mentioned ether bond is preferably 3 or more. Further, the number of carbon atoms of the fluorine-containing alkylene group having the above-mentioned ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorine-containing alkylene group having the above-mentioned ether bond is, for example, represented by the general formula:

Chemical formula

[0182] Specific examples of the fluorine-containing alkylene group having the above-mentioned ether bond include -CF2CF(CF3)OCF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n-CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. are exemplified. The fluorine-containing alkylene group having the ether bond is preferably a perfluoroalkylene group.)

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

[0184] R 2 is preferably H or an organic group of C 1-10 , more preferably H or an organic group of C 1-4 , and even more preferably H or an alkyl group of C 1-4 .

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

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

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

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

[0189] In the general formula (1a), n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1, or 2, and even more preferably 0 or 1, in terms of being able to obtain particles with a small primary particle diameter.

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

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

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

[0193] Specific examples of the monomer represented by the formula (1A) include the general formula [Chemical formula] (In the formula, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; p1 + q1 + r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, provided that when Z 3 and Z 4 are both H, p1 + q1 + r1 + s1 is not 0; A is the same as defined above). Monomers represented by the formula are included. More specifically, [Chemical formula] etc. are preferably included, and among them [Chemical formula] is preferably the case.

[0194] As the monomer represented by the general formula (1A), it is preferable that A in the formula (1A) is -COOM a , and in particular, CH2 = CFCF2OCF(CF3)COOM a , and CH2 = CFCF2OCF(CF3)CF2OCF(CF3)COOM a (In the formula, M a is the same as defined above.) At least one selected from the group consisting of is preferable, and CH2 = CFCF2OCF(CF3)COOM a is more preferable.

[0195] Also, as the monomer represented by the general formula (1), monomers represented by the following formula etc. are also included. CF2 = CFCF2 - O - Rf - A (In the formula, Rf and A are the same as above)

[0196] More specifically, [Chemical formula] etc. are included.

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

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

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

[0200] In the general formula (2), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom and may have 1 or more carbon atoms. The carbon number of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom and may have 1 or more carbon atoms. The carbon number of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As Y, -H, -F or CF3 is preferable, and -F is more preferable.

[0201] In the general formula (2), at least one of X and Y preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

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

[0203] The number of carbon atoms of the fluorine-containing alkylene group of Rf is preferably 2 or more. Further, it is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, -CF2CF2CF2-, CF2CF2CF2CF2-, etc. The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0204] The number of carbon atoms of the fluorine-containing alkylene group having the above ether bond is preferably 3 or more. Further, the number of carbon atoms of the fluorine-containing alkylene group having the above ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, and particularly preferably 5 or less. The fluorine-containing alkylene group having the above ether bond is, for example, represented by the general formula:

Chemical formula

[0205] Specific examples of the fluorine-containing alkylene group having the ether bond include -CF2CF(CF3)OCF2CF2-, -CF2CF(CF3)OCF2CF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n -CF(CF3)CH2-(wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, and the like. The fluorine-containing alkylene group having the ether bond is preferably a perfluoroalkylene group.

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

[0207] Specific examples of the fluorine-containing alkylene group having the keto group include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2CF2-, and the like. The fluorine-containing alkylene group having the keto group is preferably a perfluoroalkylene group.

[0208] Water may be added to the keto group in the fluorine-containing alkylene group. Therefore, the monomer (2) may be a hydrate. Examples of the fluorine-containing alkylene group with water added to the keto group include -CF2CF(CF3)C(OH)2-CF2-, -CF2CF(CF3)C(OH)2-CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2CF2-, and the like.

[0209] The monomer represented by the general formula (2) is preferably at least one selected from the group consisting of the monomers represented by the general formulas (2a), (2b), (2c), (2d), (2e), (2f), and (2g). CF2=CF-O-(CF2) n1 -A (2a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) CF2=CF-O-(CF2C(CF3)F) n2 -A (2b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as defined above.) CF2=CF-O-(CFX 1 ) n3 -A (2c) (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, and A is the same as defined above.) CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -A (2d) (In the formula, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and A and X 1 are the same as defined above.) CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-A (2e) (In the formula, n5 represents an integer of 0 to 10, and A and X 1 are the same as defined above.) CF2=CF-O-(CF2) n7 -O-(CF2) n8 -A (2f) (In the formula, n7 represents an integer from 1 to 10, and n8 represents an integer from 1 to 3. A is the same as the above definition.) CF2=CF[OCF2CF(CF3)] n9 O(CF2) n10 O[CF(CF3)CF2O] n11 CF(CF3)-A (2g) (In the formula, n9 represents an integer from 0 to 5, n10 represents an integer from 1 to 8, and n11 represents an integer from 0 to 5. A is the same as the above definition.)

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

[0211] Examples of the monomer represented by general formula (2a) include, for example, CF2=CF-O-CF2COOM a , CF2=CF(OCF2CF2COOM a ), CF2=CF(O(CF2)3COOM a ), CF2=CF(OCF2CF2SO3M a ), CF2=CFOCF2SO3M a , CF2=CFOCF2CF2CF2SO3M a (In the formula, M a is the same as the above definition.)

[0212] In general formula (2b), it is preferable that n2 is an integer of 3 or less in terms of the dispersion stability of the resulting composition.

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

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

[0215] Examples of the monomer represented by the general formula (2d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM a , CF2=CFOCF2CF(CF3)OCF2COOM a , CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM a , CF2=CFOCF2CF(CF3)OCF2SO3M a , CF2=CFOCF2CF(CF3)OCF2CF2SO3M a , CF2=CFOCF2CF(CF3)OCF2CF2CF2SO3M a (wherein M a represents H, NH4 or an alkali metal.)

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

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

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

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

[0220] In general formula (2g), n9 is preferably an integer of 3 or less in terms of water solubility, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, and A is -COOM a or SO3M a is preferable, and -COOM a is more preferable. M a is preferably H, Na, K or NH4.

[0221] Examples of the monomer represented by general formula (2g) include CF2=CFO(CF2)2OCF(CF3)COOM a , CF2=CFOCF2CF2OCF(CF3)CF2OCF(CF3)COOM a , CF2=CFOCF2CF(CF3)OCF2CF2OCF(CF3)COOM a , CF2=CF[OCF2CF(CF3)]2O(CF2)2O[CF(CF3)CF2O]CF(CF3)COOM a , CF2=CF[OCF2CF(CF3)]3O(CF2)2O[CF(CF3)CF2O]3CF(CF3)COOM a (wherein M a represents H, NH4 or an alkali metal.) can be mentioned.

[0222] The monomer (I) is also preferably the monomer (3) represented by general formula (3). The polymer (I) is also preferably a polymer (3) containing a polymerization unit (3) based on the monomer represented by general formula (3). CX2=CY(-Rf-A) (3) (wherein X is the same or different and is -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. A is the same as described above.)

[0223] In the production method of the present disclosure, the monomer (3) represented by the general formula (3) and other monomers may be copolymerized. The polymer (3) may be a homopolymer of the monomer represented by the general formula (3) or a copolymer with other monomers.

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

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

[0226] The monomer represented by the general formula (3) is the general formula (3a): CF2=CF-(CF2) n1 -A (3a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) The monomer represented by, and the general formula (3b): CF2=CF-(CF2C(CF3)F) n2 -A (3b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as defined above.) At least one selected from the group consisting of monomers represented by is preferred.

[0227] In the general formula (3a) and the general formula (3b), A is -SO3M a Or COOM a Is preferred, and M a Is H, a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium. R 2 Represents H or an organic group.

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

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

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

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

[0232] The monomer (I) is also preferably at least one selected from the group consisting of the monomers represented by the general formula (4a) and the general formula (4b). The polymer (I) is also preferably a polymer (4) containing a polymerization unit (4) based on at least one monomer selected from the group consisting of the monomers represented by the general formula (4a) and the general formula (4b). CF2 = CF - CF2 - O - Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4a) (where Z 1 、Z 2 and A are as defined above, Q F1 and Q F2 are the same or different and are a single bond, a fluorine-containing alkylene group which may contain an ether bond between carbon atoms, or a fluorine-containing oxyalkylene group which may contain an ether bond between carbon atoms) CF2 = CF - O - Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4b) (where Z1 , Z 2 , A, Q F1 and Q F2 is the same as the above definition)

[0233] Examples of the monomers represented by general formula (4a) and general formula (4b) include

Chemical formula

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

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

[0236] As the above-mentioned other monomer, a monomer represented by the general formula CFR=CR2 (wherein R is independently H, F, or a perfluoroalkyl group having 1 to 4 carbon atoms) is preferable. Further, as the other monomer, a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms is preferable. Examples of the other monomer include CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E form), CHF=CHCF3 (Z form), and the like. Among them, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2) is preferable in terms of good copolymerizability, and at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride is more preferable. Therefore, the polymerization unit based on the other monomer is preferably a polymerization unit based on tetrafluoroethylene. The polymerization units based on the other monomer may be the same or different in each occurrence, and the polymer (I) may contain polymerization units based on two or more different other monomers.

[0237] Examples of the other monomer also include the general formula (n1-2):

Chemical formula

[0238] Specific examples include CH2=CFCF2-O-Rf 3 , CF2=CF-O-Rf 3 , CF2=CFCF2-O-Rf 3 , CF2=CF-Rf 3 , CH2=CH-Rf 3 , CH2=CH-O-Rf 3 (In the formula, Rf 3 is the same as in the formula (n1-2)) and the like are preferably mentioned.

[0239] Examples of the other monomer also include the formula (n2-1):

Chemical formula

[0240] As the other monomer, the formula (n2-2): CH2=CHO-Rf 5 (n2-2) (wherein, Rf 5 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond and having 2 to 100 carbon atoms). Fluorine-containing vinyl ethers represented by the above formula are also included.

[0241] Specific examples of the monomer of the general formula (n2-2) include [Chemical formula] (wherein, e6 is an integer of 1 to 10), etc. are preferably included.

[0242] More specifically, [Chemical formula] etc. are included.

[0243] In addition, the general formula (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (wherein, Rf 6 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond and having 2 to 100 carbon atoms). Fluorine-containing allyl ethers represented by the above formula, the general formula (n2-4): CH2=CH-Rf 7 (n2-4) (wherein, Rf7 Examples also include fluorine-containing vinyl monomers represented by a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond with 2 to 100 carbon atoms).

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

Chemical formula

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

[0246] In the polymer (I), the content of the polymerized unit (I) is preferably, in descending order, 1.0 mol% or more, 3.0 mol% or more, 5.0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, based on all the polymerized units. It is particularly preferable that the content of the polymerized unit (I) is substantially 100 mol%, and it is most preferable that the polymer (I) consists only of the polymerized unit (I).

[0247] In polymer (I), the content of polymer units based on other monomers copolymerizable with the monomer represented by general formula (I) is preferably, in descending order, 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, based on all the polymer units. It is particularly preferable that the content of polymer units based on other monomers copolymerizable with the monomer represented by general formula (I) is substantially 0 mol%, and most preferably, polymer (I) does not contain polymer units based on other monomers.

[0248] The number average molecular weight of polymer (I) is preferably 0.1×10 4 or more, more preferably 0.2×10 4 or more, still more preferably 0.3×10 4 or more, even more preferably 0.4×10 4 or more, even more preferably 0.5×10 4 or more, particularly preferably 1.0×10 4 or more, especially particularly preferably 3.0×10 4 or more, most preferably 3.1×10 4 or more. Also, it is preferably 75.0×10 4 or less, more preferably 50.0×10 4 or less, still more preferably 40.0×10 4 or less, even more preferably 30.0×10 4 or less, particularly preferably 20.0×10 4 or less. The number average molecular weight and the weight average molecular weight are values calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. Also, when measurement by GPC is not possible, the number average molecular weight of polymer (I) can be determined from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0249] The weight average molecular weight of polymer (I) is preferably, in descending order, 0.2×10 4Above, 0.4×10 4 Above, 0.6×10 4 Above, 0.8×10 4 Above, 1.0×10 4 Above, 2.0×10 4 Above, 5.0×10 4 Above, 10.0×10 4 Above, 15.0×10 4 Above, 20.0×10 4 Above, 25.0×10 4 Above. Further, as the weight average molecular weight of the polymer (I), in descending order of preference, 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 Below.

[0250] The polymer (I) preferably has an ion exchange rate (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the polymer main chain relative to the ionic group. A precursor group that becomes ionic upon hydrolysis (for example, -SO2F) is not regarded as an ionic group for the purpose of determining the IXR.

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

[0252] As the ion exchange capacity of the polymer (I), in descending order of preference, 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.20 meq / g or more, more than 2.20 meq / g, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, 3.50 meq / g or more. The ion exchange capacity is the content of the ionic group (anionic group) of the polymer (I) and is determined by calculation from the composition of the polymer (I).

[0253] In the polymer (I), the ionic group (anionic group) is typically distributed along the polymer main chain. The polymer (I) includes the polymer main chain together with the repeating side chains bonded to this main chain, and it is preferable that these side chains have ionic groups.

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

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

[0256] The polymer (I) preferably has water solubility. Water solubility means the property of being easily dissolved or dispersed in an aqueous medium. The polymer (I) having water solubility can, for example, have its particle size unable to be measured by the dynamic light scattering method (DLS), or show a particle size of 5 nm or less.

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

[0258] The viscosity of the aqueous solution of the polymer (I) can be specified by adjusting the content of the polymer (I) in the aqueous solution to 33% by mass with respect to the aqueous solution and measuring the viscosity of the obtained aqueous solution at 20 °C using a tuning fork vibration type viscometer (model number: SV-10) manufactured by A&D Company, Limited.

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

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

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

[0262] The acid value of polymer (I) can be measured by acid - base titration after converting these groups to acid - type groups when polymer (I) has an anionic group other than an acid - type functional group, for example, -COOM a , -SO3M a , -OSO3M a or C(CF3)2OM a (M a is a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group).

[0263] Compound (II) is represented by general formula (II). General formula (II): T X -X A -R FA1 -R FA2 -X A -T X ’ (II) (In the formula, R FA1 is -Rf1 p -R F -O q - and R FA2 is -Rf 2 p -R FX -O q - and R F is a divalent fluoropolyether group, R FX is a divalent fluoropolyether group containing an anionic group, Rf 1 and Rf 2 each independently represents a C which may be substituted by one or more fluorine atoms; 1-6 is an alkylene group, Each p is independently 0 or 1; Each q is independently 0 or 1; X A each independently represents a single bond or a divalent to decavalent group, T X and T X Each of the C1-C ' groups independently contains one or more of H, O, and Cl, and does not contain the above anionic group. 24 (hydro)(fluoro)carbon groups, and (ii) at least one C1-C group containing the anionic group. 24 (hydro)(fluoro)carbon groups.

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

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

[0266] In formula (II), Rf 1and Rf 2 is, independently of one another, a C 1-6 alkylene group which may be substituted by one or more fluorine atoms.

[0267] The C 1-6 alkylene group which may be substituted by one or more fluorine atoms, the "C 1-6 alkylene group" may be linear or branched, preferably a linear or branched C 1-3 alkylene group, more preferably a linear C 1-3 alkylene group.

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

[0269] The above C 1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

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

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

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

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

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

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

[0276] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and may be, for example, 25 or more or 30 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0277] These repeating units may be linear, branched, or may contain a ring structure. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0278] The above ring structure can be a three-membered ring, four-membered ring, five-membered ring, or six-membered ring as follows. [Chemical formula] [In the formula, * indicates the bonding position.]

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

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

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

[0282] In one aspect, the repeating unit is branched.

[0283] In one aspect, R F is a group represented by any of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1, preferably 0.], -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less, the sum of c, d, e and f is 2 or more, the order of existence of each repeating unit enclosed in parentheses with c, d, e or f attached is arbitrary in the formula.], -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100.], -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [wherein, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g’ is an integer from 2 to 100, R r is [Chemical formula] (wherein, * indicates the bonding position.) is.]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [wherein, e is an integer from 1 to 200, a, b, c, d and f are each independently integers from 0 to 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula.] -(OC6F 12 )a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [wherein, f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f attached is arbitrary in the formula.]

[0284] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2) or (OCF2CF(CF3)), more preferably (OCF2CF2CF2). In one embodiment, e is 0. In another embodiment, e is 1. (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), more preferably (OCF2CF2).

[0285] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, more preferably 10 to 200. Also, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f - represented by the group. In another embodiment, the formula (f2) may be a group represented by -(OC2F4) e -(OCF2) f -.

[0286] In the above formula (f3), R 6is preferably OC2F4. In the above (f3), R 7 is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably OC3F6 or OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, but examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either linear or branched, preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g -.

[0287] In the above formula (f4), R 6 , R 7 and g have the same meanings as described in the above formula (f3) and have the same embodiments. R 6’ , R 7’ and g' each have the same meanings as R 6 , R 7 and g described in the above formula (f3) and have the same embodiments. R r is preferably

Chemical formula

[0288] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0289] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

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

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

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

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

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

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

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

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

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

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

[0300] R FX The above fluoropolyether group in may be a group in which one or more hydrogen atoms of the polyether group are substituted with fluorine atoms, and is preferably a perfluoropolyether group.

[0301] R FX has, as a repeating unit, (a1)-CF2CF(G x )O- (b1)-CF(G x )O- (c1)-CF2(CF2) x1 CF(G x )(CF2) x2 O-(where X1 and X2 are zero or integers from 1 to 2, provided that X1 + X2 is at least 1) [Here, G x is a C1-C5 perfluoro(oxy)alkylene group containing at least one anionic group as detailed above] and is preferably a divalent fluoropolyether group having a unit selected from the group consisting of

[0302] Note that the order of existence of the repeating units constituting R F and R FX is arbitrary.

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

[0304] In formula (II), X A is understood as a linker connecting the fluoropolyether moiety (R FA1 and R FA2 ) and the moiety containing an anionic group (T X and T X '). Therefore, the X A may be a single bond or any group as long as the compound represented by formula (II) can exist stably.

[0305] X AEach is independently a single bond or a divalent to decavalent group.

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

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

[0308] The divalent to decavalent group in the above X A is preferably a divalent to octavalent group. In one embodiment, such a divalent to decavalent group is preferably a divalent to tetravalent group, more preferably a divalent group. In another embodiment, such a divalent to decavalent group is preferably a trivalent to octavalent group, more preferably a trivalent to hexavalent group.

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

[0310] The above divalent group is preferably an oxygen atom, a sulfur atom, NH, CO, or a divalent organic group, more preferably an oxygen atom or a divalent organic group, still more preferably a divalent organic group.

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

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

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

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

[0315] In one embodiment, X A is, for example, a single bond or the following formula: -(R 51) p5 -(X 51 ) q5 - [wherein: R 51 represents a single bond, -(CH2) s5 - or an o-, m- or p-phenylene group, preferably -(CH2) s5 -, s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2, X 51 represents -(X 52 ) l5 -, X 52 each independently represents -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -, -O-CONR 54 -, -NR 54 - and -(CH2) n5 - and represents a group selected from the group consisting of, R 53 each independently represents a phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group, preferably a phenyl group or C 1-6 alkyl group, more preferably a methyl group, R 54 each independently represents a hydrogen atom, a phenyl group or C 1-6 alkyl group (preferably a methyl group), m5 is, in each occurrence, independently an integer from 1 to 100, preferably an integer from 1 to 20, n5 is, in each occurrence, independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, l5 is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the order of presence of each repeating unit enclosed in parentheses with p5 or q5 is arbitrary, with the right side being T X and T X ' is bonded.] Examples of the divalent organic group represented by this formula include. Here, X A (typically the hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred embodiment, X A is not substituted with these groups.

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

[0317] Preferably, the above X A are each independently a single bond, a C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 5 - [wherein, R 51 and R 52 are as defined above, and X 53 is -O-, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -Si(R 53 )2-, -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -O-(CH2) u5 -Si(R 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2-, -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2-, -CONR 54 -(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 53 )2- (wherein, R 53 , R 54 and m5 are as defined above, and u5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3.) represents, X 54 is, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (wherein each symbol has the same meaning as defined above.) represents.] can be.

[0318] More preferably, the above X A are each independently a single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 (-), -(CH2) s5 -X 53 -(CH2) t5 (-), -X 54 (-), or -X 54 -(CH2) t5 (-), [wherein X 53 , X 54 , s5 and t5 have the same meaning as defined above.] is.

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

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

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

[0322] In one aspect, the above X A are each independently a single bond, C 1-20 an alkylene group, -(CH2) s5 -O-(CH2) t5 -, -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, or -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [In the formula, R 53 , m5, s5, t5 and u5 have the same meanings as above, and v is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. It is.

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

[0324] The above X A are each independently a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably, C1-3 may be substituted by one or more substituents selected from (perfluoroalkyl group). In one embodiment, X A is unsubstituted.

[0325] In one embodiment, X A is each independently -O-C 1-6 and may be other than an alkylene group.

[0326] In another embodiment, examples of X A include the following groups:

Chemical formula

Chemical formula

Chemical formula

[0327] Specific examples of the above X A are, for example: a single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -CH2OCF2CHFOCF2-, -CH2OCF2CHFOCF2CF2-, -CH2OCF2CHFOCF2CF2CF2-, -CH2OCH2CF2CF2OCF2-, -CH2OCH2CF2CF2OCF2CF2-, -CH2OCH2CF2CF2OCF2CF2CF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -(CH2)5-、 -(CH2)6-、 -CO-、 -CONH-、 -CONH-CH2-、 -CONH-(CH2)2-、 -CONH-(CH2)3-、 -CONH-(CH2)4-、 -CONH-(CH2)5-、 -CONH-(CH2)6-、 -CON(CH3)-CH2-、 -CON(CH3)-(CH2)2-、 -CON(CH3)-(CH2)3-、 -CON(CH3)-(CH2)4-、 -CON(CH3)-(CH2)5-、 -CON(CH3)-(CH2)6-、 -CON(Ph)-CH2- (where Ph means phenyl), -CON(Ph)-(CH2)2- (where Ph means phenyl), -CON(Ph)-(CH2)3- (where Ph means phenyl), -CON(Ph)-(CH2)4- (where Ph means phenyl), -CON(Ph)-(CH2)5- (where Ph means phenyl), -CON(Ph)-(CH2)6- (where Ph means phenyl), -CONH-(CH2)2NH(CH2)3-、 -CONH-(CH2)6NH(CH2)3-、 -CH2O-CONH-(CH2)3-、 -CH2O-CONH-(CH2)6-、 -S-(CH2)3-、 -(CH2)2S(CH2)3-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、 -C(O)O-(CH2)3-、 -C(O)O-(CH2)6-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、 -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、 -OCH2-、 -O(CH2)3-、 -OCFHCF2-、

Chem.

Chem.

[0328] In yet another aspect, X A is, independently of each other, a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 -. In the formula, x1, y1 and z1 are, independently of each other, integers from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

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

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

[0331] In the above formula, each R 17 is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0332] In addition, the above X A is such that the left side of each formula is bonded to R FA1 or R FA2 , and the right side is bonded to T X and T X '.

[0333] In yet another aspect, examples of X A include the following groups:

Chemical formula

Chemical formula

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

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

[0336] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include [Chemical formula] and the like.

[0337] In this embodiment, X A can each independently be a group having a valence of 3 to 10.

[0338] In yet another embodiment, examples of X A include the following groups: [Chemical formula] [wherein, R 25 , R 26 and R 27 are each independently an organic group having a valence of 2 to 6, R 25 is bonded to at least one R FA1 or R FA2 , R 26 and R 27 are each bonded to at least one R Si .]

[0339] In one embodiment, R 25 is a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, a C 5-20 arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -. In the above, R 57 and R 59 are each independently a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, or a C 5-20 arylene group. The above X 58 is -O-, -S-, -CO-, -O-CO- or -COO-.

[0340] In one embodiment, R 26 and R 27 are each independently a hydrocarbon or a group having at least one atom selected from N, O, and S in the end or main chain of the hydrocarbon, preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-, etc. Here, R 36 are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R 37 is N, O, or S, preferably N or O. R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 - or -R 45 -R 46 -. Here, R 45 are each independently an alkyl group having 1 to 6 carbon atoms. R 46 is N, O, or S, preferably O.

[0341] In this embodiment, X A can each independently be a 3- to 10-valent group.

[0342] In yet another embodiment, X A is as follows:

Chemical formula

[0343] The above X a is a single bond or a divalent linking group directly bonded to the isocyanuric ring. X aAs for this, a divalent group containing at least one bond selected from the group consisting of a single bond, an alkylene group, or an ether bond, an ester bond, an amide bond, and a sulfide bond is preferable, and a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond is more preferable.

[0344] X a As for this, the following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (In the formula, X 121 ~X 124 are each independently H, F, OH, or -OSi(OR 121 )3 (in the formula, the three R 121 are each independently an alkyl group having 1 to 4 carbon atoms.), and the above X a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is bonded to CX 121 X 122 ). x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.) A group represented by is more preferable.

[0345] As for the above X a1 , -O- or -C(=O)O- is preferable.

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

[0347] The above X a is not particularly limited, but specifically,[[]] -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, -(CF2) n5 -(n5 is an integer of 0 to 4), -(CF2) n5 -(CH2) m5 -(n5 and m5 are each independently an integer of 0 to 4), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- etc. can be mentioned.

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

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

[0350] The compound (II) is not particularly limited, but can have a number average molecular weight of 5×10 2 ~1×10 5 It can have a number average molecular weight of. Among such ranges, it is preferable from the viewpoint of polymerization stability to have a number average molecular weight of preferably 2,000 or more, more preferably 2,500 or more as the lower limit, and preferably 32,000 or less, more preferably 12,000 or less as the upper limit. The number average molecular weight of the compound (II) is 19 a value measured by 19F-NMR.

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

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

[0353] Examples of the compound (II) include the compounds described in International Publication No. 2019 / 048394.

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

[0355] The content of the above polymer compound in the TFE-based polymer composition is determined by solid NMR measurement. In addition, the measurement methods of the respective polymers are described in International Publication No. 2014 / 099453, International Publication No. 2010 / 075497, International Publication No. 2010 / 075496, International Publication No. 2011 / 008381, International Publication No. 2009 / 055521, International Publication No. 1987 / 007619, Japanese Patent Application Laid-Open No. 61-293476, International Publication No. 2010 / 075494, International Publication No. 2010 / 075359, International Publication No. 2012 / 082454, International Publication No. 2006 / 119224, International Publication No. 2013 / 085864, International Publication No. 2012 / 082707, International Publication No. 2012 / 082703, International Publication No. 2012 / 082451, International Publication No. 2006 / 135825, International Publication No. 2004 / 067588, International Publication No. 2009 / 068528, Japanese Patent Application Laid-Open No. 2004-075978, Japanese Patent Application Laid-Open No. 2001-226436, International Publication No. 1992 / 017635, International Publication No. 2014 / 069165, Japanese Patent Application Laid-Open No. 11-181009, etc. As the measurement method of the content of the above polymer compound, the measurement methods of the respective polymers described therein can be used.

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

[0357] The TFE-based polymer composition of the present disclosure preferably contains substantially no moisture. Thereby, generation of gas and deterioration of the characteristics of the electrochemical device can be suppressed. In addition, since the electrode active material and the solid electrolyte to be combined can be widely selected, it is advantageous in terms of the production process. Substantially no moisture means that the moisture content with respect to the above TFE-based polymer composition is 0.010% by mass or less. The above moisture content is preferably 0.005% by mass or less, more preferably 0.003% by mass or less, still more preferably 0.002% by mass or less, and even more preferably 0.001% by mass or less. The above moisture content is measured by the following method. Measure the mass of the TFE-based polymer composition before and after heating at 150 °C for 2 hours, and calculate according to the following formula. Take the sample three times, calculate each time, then find the average, and adopt the average value. Moisture content (% by mass) = [(mass (g) of the TFE-based polymer composition before heating) - (mass (g) of the TFE-based polymer composition after heating)] / (mass (g) of the TFE-based polymer composition before heating) × 100

[0358] The TFE-based polymer composition of the present disclosure may have a 1.0% mass loss temperature of 492 °C or lower. 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. The above 1.0% mass loss temperature is a value measured by the following method. Precisely weigh about 10 mg of a TFE-based polymer composition having no heating history at a temperature of 300 °C or higher, store it in a dedicated aluminum pan, and measure TG·DTA (differential thermal and thermogravimetric simultaneous measurement device). The 1.0% mass loss temperature is the temperature corresponding to the point where the weight has decreased by 1.0 mass% when the temperature of the aluminum pan is raised from 25 °C to 600 °C at a rate of 10 °C / min in an air atmosphere.

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

[0360] The TFE-based polymer composition of the present disclosure preferably has an endothermic peak temperature of 333°C or higher, more preferably 335°C or higher, still more preferably 337°C or higher, even more preferably 340°C or higher, and also preferably 350°C or lower, more preferably 346°C or lower, in that it can form a sizing sheet with even better strength. The above endothermic peak temperature is the temperature corresponding to the minimum point in the melting heat curve obtained by performing differential scanning calorimetry [DSC] on a TFE-based polymer composition having no heating history at a temperature of 300°C or higher at a heating rate of 10°C / min. When there are two or more minimum points in one melting peak, each is taken as the endothermic peak temperature.

[0361] The TFE-based polymer composition of the present disclosure preferably has a melting point of 315°C or higher, more preferably 320°C or higher, still more preferably 323°C or higher, even more preferably 325°C or higher, and also preferably 335°C or lower, more preferably 330°C or lower, in that it can form a sizing sheet with even better strength. The above melting point is the temperature corresponding to the minimum point in the melting heat curve obtained by performing differential scanning calorimetry [DSC] on a TFE-based polymer composition having a heating history at a temperature of 300°C or higher at a heating rate of 10°C / min.

[0362] The TFE-based polymer composition of the present disclosure preferably has a standard specific gravity (SSG) of 2.280 or less, more preferably 2.250 or less, still more preferably 2.220 or less, even more preferably 2.200 or less, even more preferably 2.190 or less, particularly preferably 2.180 or less, and most preferably 2.170 or less, in that it can form a composite sheet with even better strength. The above SSG is preferably also 2.130 or more, and may be 2.140 or more, or may be 2.150 or more. The above SSG is measured by the water displacement method in accordance with ASTM D 792 using a sample molded in accordance with ASTM D 4895 89.

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

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

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

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

[0367] The above emulsion polymerization can be carried out, for example, in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator. In the above emulsion polymerization, an aqueous medium, the above anionic fluorine-containing surfactant, monomers and, if necessary, other additives are charged into a polymerization reactor, the contents of the reactor are stirred, and the reactor is maintained at a predetermined polymerization temperature. Then, a predetermined amount of a polymerization initiator is added to initiate the polymerization reaction. After the start of the polymerization reaction, monomers, a polymerization initiator, a chain transfer agent, the above surfactant, etc. may be additionally added according to the purpose.

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

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

[0370] The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide. For example, dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxy esters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, etc. Also, di(ω-hydroxy-dodecafluorooctanoyl) peroxide, di(ω-hydroxy-tetradecafluoroheptanoyl) peroxide, di(ω-hydroxy-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di(ω-chloro-hexafluorobutyryl) peroxide, di(ω-chloro-decafluorohexanoyl) peroxide, di(ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydroxy-dodecafluorooctanoyl-ω-hydroxy-hexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydroxy-dodecafluorooctanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl) peroxide, di(trichlorooctafluorohexanoyl) peroxide, di(tetrachloroundecafluorooctanoyl) peroxide, di(pentachlorotetradecafluorodecanoyl) peroxide, di(undecachlorodotriacontapentafluorodocosanoyl) peroxide, and di[perfluoro(or fluorochloro)acyl] peroxides, etc. are listed as typical ones.

[0371] The water-soluble radical polymerization initiator may be a known water-soluble peroxide. For example, ammonium salts, potassium salts, sodium salts of persulfuric acid, perboric acid, perchloric acid, phosphoric acid, percarbonic acid, etc., t-butyl permaleate, t-butyl hydroperoxide, succinic acid peroxide, etc. may be mentioned. Among them, ammonium persulfate and succinic acid peroxide are preferred. Reducing agents such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.

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

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

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

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

[0376] The redox initiator is particularly preferably a combination of an oxidizing agent that is a salt and a reducing agent that is a salt. For example, the oxidizing agent that is a salt is more preferably at least one selected from the group consisting of persulfate, permanganate, cerium(IV) salt, and bromate, even more preferably permanganate, and particularly preferably potassium permanganate. Also, the reducing agent that is a salt is more preferably at least one selected from the group consisting of oxalate, malonate, succinate, glutarate, and bromate, even more preferably oxalate, and particularly preferably ammonium oxalate.

[0377] Specific examples of the redox initiator preferably include at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, manganese triacetate / ammonium oxalate, and ammonium cerium nitrate / ammonium oxalate. More preferably, it is at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, and ammonium cerium nitrate / ammonium oxalate. Even more preferably, it is potassium permanganate / oxalic acid.

[0378] When using a redox initiator, the oxidizing agent and the reducing agent may be added together at the initial stage of polymerization, or the reducing agent may be added together at the initial stage of polymerization and the oxidizing agent may be added continuously, or the oxidizing agent may be added together at the initial stage of polymerization and the reducing agent may be added continuously, or both the oxidizing agent and the reducing agent may be added continuously.

[0379] When adding one of the redox polymerization initiators first and then continuously adding the other during the initial stage of polymerization, it is preferable to gradually reduce the addition rate in terms of obtaining a TFE-based polymer with a low SSG, and it is more preferable to stop the polymerization during the process. The preferable time to stop the addition is before 20 to 40% by mass of the total TFE consumed in the polymerization reaction is consumed.

[0380] When using a redox initiator as the polymerization initiator, for the aqueous medium, the addition amount of the oxidizing agent is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, still more preferably 0.5 ppm or more, even more preferably 1 ppm or more, particularly preferably 5 ppm or more, and extremely preferably 10 ppm or more. Also, it is preferably 10000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and even more preferably 50 ppm or less. The addition amount of the reducing agent is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, still more preferably 3 ppm or more, even more preferably 5 ppm or more, particularly preferably 10 ppm or more. Also, it is preferably 10000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and even more preferably 50 ppm or less. Also, when using a redox initiator in the above emulsion polymerization, the polymerization temperature is preferably 100 °C or lower, more preferably 95 °C or lower, and still more preferably 90 °C or lower. Also, it is preferably 10 °C or higher, more preferably 20 °C or higher, and still more preferably 30 °C or higher.

[0381] As the above polymerization initiator, a water-soluble radical polymerization initiator and a redox initiator are preferable in terms of easily obtaining each of the above physical properties.

[0382] The above aqueous medium is a reaction medium for carrying out the polymerization and means a liquid containing water. The above aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as alcohol, ether, or ketone, and / or a fluorine-containing organic solvent having a boiling point of 40 °C or lower.

[0383] In the above emulsion polymerization, a nucleating agent, a chain transfer agent, a buffer, a pH adjuster, a stabilization aid, a dispersion stabilizer, a radical scavenger, a decomposer of the polymerization initiator, a dicarboxylic acid, etc. may be used as necessary.

[0384] For the purpose of adjusting the particle size, it is preferable to perform the above emulsion polymerization by adding a nucleating agent. It is preferable to add the nucleating agent before the start of the polymerization reaction. As the above nucleating agent, known ones can be used. For example, it is preferably at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents, and more preferably a nonionic surfactant.

[0385] Examples of the above fluoropolyether include perfluoropolyether (PFPE) acid or its salt. The above perfluoropolyether (PFPE) acid or its salt may have an arbitrary chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Also, two or more types of fluorocarbon groups may be present in the molecule. A typical structure has a repeating unit represented by the following formula: (-CFCF3-CF2-O-) n (-CF2-CF2-CF2-O-) n (-CF2-CF2-O-) n -(-CF2-O-) m (-CF2-CFCF3-O-) n -(-CF2-O-) m

[0386] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed in this document, the above PFPE acid or its salt may have a carboxylic acid group or its salt at one or both ends. The above PFPE acid or its salt may also have a sulfonic acid, phosphonic acid group or their salts at one or both ends. Also, the above PFPE acid or its salt may have different groups at each end. For monofunctional PFPE, the other end of the molecule is usually perfluorinated, but may contain hydrogen or chlorine atoms. The above PFPE acid or its salt has at least two ether oxygens, preferably at least four ether oxygens, even more preferably at least six ether oxygens. Preferably, at least one of the fluorocarbon groups separating the ether oxygens, more preferably at least two of such fluorocarbon groups, has 2 or 3 carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. Also, preferably, the above PFPE acid or its salt has a total of at least 15 carbon atoms. For example, the preferred minimum value of n or n + m in the above repeating unit structure is at least 5. Two or more of the above PFPE acids or their salts having an acid group at one or both ends can be used in the production method of the present disclosure. The above PFPE acid or its salt preferably has a number average molecular weight of less than 6000 g / mol.

[0387] In terms of being able to further increase the molecular weight of the TFE-based polymer and improve the strength of the composite sheet, the above emulsion polymerization is preferably carried out by adding a radical scavenger or a decomposer of the polymerization initiator. The above radical scavenger or decomposer of the polymerization initiator is preferably added after the start of the polymerization reaction, preferably before 10% by mass or more, preferably 20% by mass or more of the total TFE consumed in the polymerization reaction is polymerized, and also preferably before 50% by mass or less, preferably 40% by mass or less is polymerized. When depressurization and repressurization described later are carried out, it is preferably added thereafter.

[0388] As the radical scavenger, a compound having no restart ability after addition to or chain transfer with free radicals in the polymerization system is used. Specifically, a compound that easily undergoes a chain transfer reaction with primary radicals or growing radicals and then generates stable radicals that do not react with monomers, or a compound having a function of easily undergoing an addition reaction with primary radicals or growing radicals to generate stable radicals is used. What is generally called a chain transfer agent is characterized by its activity in terms of the chain transfer constant and the restart efficiency. Among chain transfer agents, those with a restart efficiency of almost 0% are called radical scavengers. The above radical scavenger can also be, for example, a compound whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant and whose restart efficiency is substantially zero%. "The restart efficiency is substantially zero%" means that the generated radicals are converted into stable radicals by the radical scavenger. Preferably, it is a compound whose chain transfer constant (Cs) (= chain transfer rate constant (kc) / polymerization rate constant (kp)) with TFE at the polymerization temperature is greater than 0.1. For the above compound, it is more preferable that the chain transfer constant (Cs) is 0.5 or more, still more preferable that it is 1.0 or more, even more preferable that it is 5.0 or more, and particularly preferable that it is 10 or more.

[0389] As the above radical scavenger, for example, at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N - diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl2) is preferable. Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m - or p - salicylic acid, gallic acid, naphthol, etc. Examples of the above unsubstituted phenol include о -, m - or p - nitrophenol, о -, m - or p - aminophenol, p - nitrosophenol, etc. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, naphthoresorcinol, etc. Examples of the aromatic amines include o-, m- or p-phenylenediamine, benzidine and the like. Examples of the quinone compounds include o-, m- or p-benzoquinone, 1,4-naphthoquinone, alizarin and the like. Examples of the thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN) and the like. Among the above radical scavengers, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

[0390] From the viewpoint of moderately reducing the standard specific gravity, the addition amount of the above radical scavenger is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration. A more preferable lower limit is 10% (molar basis), and even more preferably 15% (molar basis). A more preferable upper limit is 400% (molar basis), and even more preferably 300% (molar basis).

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

[0392] The above emulsion polymerization may be carried out in the presence of 5 to 500 ppm of dicarboxylic acid with respect to the aqueous medium in order to reduce the amount of coagulum generated during the polymerization, and it is preferably carried out in the presence of 10 to 200 ppm of dicarboxylic acid. If the above dicarboxylic acid is too little with respect to the aqueous medium, there is a risk that a sufficient effect cannot be obtained. If it is too much, a chain transfer reaction may occur, and the resulting polymer may have a low molecular weight. More preferably, the above dicarboxylic acid is 150 ppm or less. The above dicarboxylic acid may be added before the start of the polymerization reaction or during the polymerization.

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

[0394] In the above emulsion polymerization, the polymerization temperature and the polymerization pressure are appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, and the reaction rate. Usually, the polymerization temperature is 5 to 150 °C, preferably 10 °C or higher, more preferably 30 °C or higher, and even more preferably 50 °C or higher. Also, more preferably, it is 120 °C or lower, and even more preferably 100 °C or lower. The polymerization pressure is 0.05 to 10 MPaG. More preferably, the polymerization pressure is 0.3 MPaG or higher, and even more preferably 0.5 MPaG or higher. Also, more preferably, it is 5.0 MPaG or lower, and even more preferably 3.0 MPaG or lower.

[0395] When using VDF as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the VDF concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.001 mol% or more, and more preferably 0.01 mol% or more. The above concentration may be 15 mol% or less, preferably 6.0 mol% or less, more preferably 5.0 mol% or less, even more preferably 3.0 mol% or less, and particularly preferably 1.0 mol% or less. The above VDF concentration may be maintained until the end of the polymerization reaction, or pressure reduction may be carried out during the process. VDF is preferably charged all at once before the start of polymerization, but a part may be added continuously or intermittently after the start of polymerization.

[0396] When using VDF as the modified monomer, in the above emulsion polymerization, after charging VDF into the polymerization vessel, it is preferable not to perform pressure reduction until the polymerization is completed. Thereby, VDF can be left in the system until the end of polymerization, and the strength of the composite sheet using the obtained TFE-based polymer can be further increased.

[0397] When using HFP as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the HFP concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.01 to 3.0 mol%. Further, when 40% by mass of all the TFE consumed in the polymerization reaction is polymerized, the HFP concentration in the gas in the reactor is preferably greater than 0 mol% and 0.2 mol% or less. The above HFP concentration is preferably maintained until the end of the polymerization reaction. HFP may be charged all at once before the start of polymerization, or a part may be charged before the start of polymerization and continuously or intermittently added after the start of polymerization. By ensuring that HFP remains until the end of the polymerization reaction, although the strength of the composite sheet using the obtained TFE-based polymer is high, the extrusion pressure decreases.

[0398] When using HFP as the modified monomer, in the above emulsion polymerization, in terms of further improving the strength of the coating sheet using the obtained TFE-based polymer, it is preferable to depressurize before 5 to 40% by mass of the total TFE consumed in the polymerization reaction is polymerized, and then repressurize only with TFE. The above depressurization is preferably carried out so that the pressure in the reactor becomes 0.2 MPaG or less, more preferably so that it becomes 0.1 MPaG or less, and even more preferably so that it becomes 0.05 MPaG or less. Also, it is preferably carried out so that it becomes 0.0 MPaG or more. Also, the above depressurization and repressurization may be carried out multiple times. The depressurization may be carried out to a reduced pressure using a vacuum pump.

[0399] When using CTFE as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, it is preferable that the CTFE concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is 0.001 mol% or more, and more preferably 0.01 mol% or more. The above concentration is preferably 3.0 mol% or less, and more preferably 1.0 mol% or less. The above CTFE concentration may be maintained until the end of the polymerization reaction, or depressurization may be carried out during the process. CTFE is preferably charged all at once before the start of polymerization, but a part may be added continuously or intermittently after the start of polymerization.

[0400] When using CTFE as the modified monomer, in the above emulsion polymerization, after charging CTFE into the polymerization vessel, it is preferable not to carry out depressurization until the polymerization is completed. Thereby, CTFE can be left in the system until the end of polymerization, and the strength of the coating sheet using the obtained TFE-based polymer can be further increased.

[0401] Step (A) is also preferably Step (A2) of obtaining an aqueous dispersion of a TFE-based polymer by emulsion polymerizing TFE in an aqueous medium in the presence of a hydrocarbon-based surfactant.

[0402] The hydrocarbon-based surfactant preferably has 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all) of the hydrogen atoms bonded to carbon atoms substituted with fluorine atoms.

[0403] Step (A2) preferably includes a step of performing emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of a specific hydrocarbon-based surfactant, and a step of continuously adding the specific hydrocarbon-based surfactant in the above step.

[0404] The continuous addition of the specific hydrocarbon-based surfactant means, for example, adding the specific hydrocarbon-based surfactant not all at once, but over time, continuously or in portions. The specific hydrocarbon-based surfactant is, for example, a hydrocarbon-based surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), or a hydrocarbon-based surfactant obtained by subjecting a hydrocarbon-based surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group) to radical treatment or oxidation treatment. The above radical treatment may be any treatment that generates radicals in a hydrocarbon-based surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). For example, deionized water and a hydrocarbon-based surfactant are added to a reactor, the reactor is sealed, the system is purged with nitrogen, the reactor is heated and pressurized, a polymerization initiator is charged, stirred for a certain period of time, and then the reactor is depressurized until it reaches atmospheric pressure and cooled. The above oxidation treatment is a treatment in which an oxidizing agent is added to a hydrocarbon-based surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group). Examples of the oxidizing agent include oxygen, ozone, hydrogen peroxide solution, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, etc. By the above production method, a TFE-based polymer having a molecular weight equivalent to that of a production method using a conventional fluorine-containing surfactant can be produced without using a conventional fluorine-containing surfactant.

[0405] In the above manufacturing method, in the step of continuously adding the specific hydrocarbon surfactant, it is preferable that the addition of the hydrocarbon surfactant to the aqueous medium is started when the solid content of the TFE-based polymer formed in the aqueous medium is less than 0.60% by mass. When it is 0.5% by mass or less, it is preferable that the addition of the specific hydrocarbon surfactant to the aqueous medium is started. It is more preferable that the specific hydrocarbon surfactant is started to be added when the solid content is 0.3% by mass or less, still more preferable when it is 0.2% by mass or less, even more preferable when it is 0.1% by mass or less, and particularly preferable to start adding at the same time as the polymerization initiation. The solid content is the concentration with respect to the total of the aqueous medium and the TFE-based polymer.

[0406] In the step of continuously adding the specific hydrocarbon surfactant, the addition amount of the specific hydrocarbon surfactant is preferably 0.01 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.05% by mass, a still more preferable lower limit is 0.1% by mass, a more preferable upper limit is 5% by mass, and a still more preferable upper limit is 1% by mass.

[0407] In the step of performing emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant is preferably large, and is preferably 0.0001 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If it is less than 0.0001% by mass, the dispersing power may be insufficient, and if it exceeds 10% by mass, an effect commensurate with the amount cannot be obtained, and instead, the polymerization rate may decrease or the reaction may stop. The amount of the specific hydrocarbon surfactant is appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, etc.

[0408] As the specific hydrocarbon surfactant, the formula: R-X (wherein R is a fluorine-free organic group having 1 to 2000 carbon atoms and having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), and X is -OSO3X 1 , -COOX 1 or -SO3X 1 (X 1 is H, a metal atom, NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 1 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.)) is preferred. R preferably has 500 or less carbon atoms, more preferably 100 or less carbon atoms, still more preferably 50 or less carbon atoms, and still more preferably 30 or less carbon atoms. As the specific hydrocarbon surfactant, the following formula (a):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

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

[0410] In formula (a), R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the above alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Also, when the above alkyl group has 2 or more carbon atoms, the carbonyl group may be included at the end of the above alkyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the above alkyl group. In addition, when the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable, and examples thereof include a furan ring. R 1a In, a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the end and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the end of the above alkyl group.

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

[0412] The hydrogen atom bonded to the carbon atom of the above alkyl group may be substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing the above ester bond include a group represented by the formula: -O-C(=O)-R 101a (wherein R 101a is an alkyl group). The above alkyl group may have up to 75% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have up to 50% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have up to 25% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0413] In the formula, R 2a and R 3a are each independently a single bond or a divalent linking group. R 2a and R 3a are each independently preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms. R 2a and R 3a The above alkylene group constituting is preferably free of a carbonyl group.

[0414] The above alkylene group may have the hydrogen atoms bonded to the carbon atoms substituted by a functional group, for example, may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but is preferably not substituted by any functional group. Examples of the above monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102a (In the formula, R 102a is an alkyl group). The above alkylene group may have up to 75% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have up to 50% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have up to 25% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0415] R 1a , R 2a and R 3aThe total number of carbon atoms is 6 or more. As the total number of carbon atoms, 8 or more is preferable, 9 or more is more preferable, 10 or more is still more preferable, 20 or less is preferable, 18 or less is more preferable, and 15 or less is still more preferable. R 1a 、R 2a and R 3a Any two of them may be bonded to each other to form a ring.

[0416] In formula (a), X a is H, a metal atom, NR 4a 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 4a is H or an organic group (preferably an organic group not containing fluorine). The four R 4a may be the same or different. As the organic group in R 4a , an alkyl group is preferable. As R 4a , H or an organic group having 1 to 10 carbon atoms is preferable, H or an organic group having 1 to 4 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is still more preferable. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferable. X a is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4a 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferable. Since it is still more easily soluble in water, Na, K or NH4 is still more preferable. Na or NH4 is particularly preferable. Since it is easily removable, NH4 is most preferable. When X a is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in the TFE-based polymer or the final product.

[0417] R 1aExamples include linear or branched alkyl groups having 1 to 8 carbon atoms and not containing a carbonyl group, cyclic alkyl groups having 3 to 8 carbon atoms and not containing a carbonyl group, linear or branched alkyl groups having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, cyclic alkyl groups having 3 to 45 carbon atoms and containing a carbonyl group, or alkyl groups containing a monovalent or divalent heterocyclic ring having 3 to 45 carbon atoms.

[0418] Examples of the surfactant (a) include the following surfactants. In each formula, X a is as described above.

[0419] [Chemical formula]

[0420] [Chemical formula]

[0421] [Chemical formula]

[0422] [Chemical formula]

[0423] [Chemical formula]

[0424] [Chemical formula]

[0425] [Chemical formula]

[0426] [Chemical formula]

[0427] The surfactant (a) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

[0429] In formula (b), R 1b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring and the like can be mentioned. In R 1b , a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the end and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the end of the above alkyl group.

[0430] In this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the above heterocyclic ring.

[0431] R 1b The above substituents that the alkyl group as R may have are preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0432] R 1b The above alkyl group as R preferably does not contain a carbonyl group. The above alkyl group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, or may have 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0433] R 1b Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents. Even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. Particularly preferably, it is a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably, it is a methyl group (-CH3).

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

[0435] R 2b and R 4b As the above substituents, halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms or cyclic alkyl groups having 3 to 10 carbon atoms, and hydroxy groups are preferable, and a methyl group and an ethyl group are particularly preferable.

[0436] R 2b and R 4b The above alkyl group preferably does not contain a carbonyl group. The above alkyl group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, or may have 25% or less substituted by halogen atoms, but is preferably an unhalogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0437] R 2b and R 4b As the above alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms without substituents is even more preferred, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred.

[0438] R 2b and R 4b are each independently preferably H or a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group, more preferably H or a linear or branched alkyl group having 1 to 3 carbon atoms without substituents, even more preferably H, a methyl group (-CH3) or an ethyl group (-C2H5), and particularly preferably H.

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

[0440] The above alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0441] The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group, or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, and even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and even more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

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

[0443] In formula (b), n is an integer of 1 or more. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, still more preferably an integer of 5 to 25, and particularly preferably an integer of 5 to 9 or 11 to 25.

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

[0445] n, p, and q are preferably integers whose sum is 5 or more. More preferably, the sum of n, p, and q is an integer of 8 or more. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0446] In formula (b), X b is H, a metal atom, NR 5b 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 5b is H or an organic group (preferably an organic group not containing fluorine). The four Rs 5b may be the same or different. As the organic group in R 5b , an alkyl group is preferred. As R 5b , H or an organic group having 1 to 10 carbon atoms is preferred, H or an organic group having 1 to 4 carbon atoms is more preferred, and H or an alkyl group having 1 to 4 carbon atoms is still more preferred. Examples of the above metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. X b is a metal atom or NR 5b 4 (R 5b is as described above) may be. X b is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 5b 4. Since it is easily soluble in water, H, Na, K, Li, or NH4 is more preferred. Since it is even more easily soluble in water, Na, K, or NH4 is still more preferred. Na or NH4 is particularly preferred. Since it is easily removed, NH4 is most preferred. When X b is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for metal components to remain in the TFE-based polymer or the final product.

[0447] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6bCO-B-*, or -CO- (provided that -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b excluding the carbonyl group contained in CO-B-.), where B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6b is preferably H or a methyl group. * indicates the side bonded to -OSO3X b in the formula.

[0448] L is preferably a single bond.

[0449] As the surfactant (b), the following formula:

Chemical formula

[0450] Examples of the surfactant (b) include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, etc. can be mentioned.

[0451] The surfactant (b) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

[0453] In formula (c), R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the above alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Also, when the above alkyl group has 2 or more carbon atoms, the above carbonyl group can also be included at the end of the above alkyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the above alkyl group. Further, when the above alkyl group has 3 or more carbon atoms, it can also contain a monovalent or divalent heterocyclic ring or can form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring, etc. can be mentioned. R 1c In, a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the end and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the end of the above alkyl group.

[0454] In the present specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0455] The above alkyl group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 101c (wherein R 101c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0456] In formula (c), R 2c and R 3c are each independently a single bond or a divalent linking group. R 2c and R 3c are each independently preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms. R 2c and R 3c The above alkylene group constituting them preferably does not contain a carbonyl group.

[0457] The above alkylene group may have a hydrogen atom bonded to a carbon atom substituted by a functional group, for example, may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102c (In the formula, R 102c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0458] R 1c 、R 2c and R 3c have a total carbon number of 5 or more. As the total carbon number, 7 or more is preferable, 9 or more is more preferable, 20 or less is preferable, 18 or less is more preferable, and 15 or less is still more preferable. R 1c 、R 2c and R 3c Any two of them may be bonded to each other to form a ring.

[0459] In formula (c), A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and R 4c is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.). R 4c The organic group in is preferably an alkyl group. R 4cPreferably, it is H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include an alkali metal (Group 1) and an alkaline earth metal (Group 2), and Na, K, or Li is preferable. X c Preferably, it is H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 4c 4, and since it is easily soluble in water, H, Na, K, Li, or NH4 is more preferable, and since it is still more easily soluble in water, Na, K, or NH4 is still more preferable, Na or NH4 is particularly preferable, and since it is easily removed, NH4 is most preferable. X c When X is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in the TFE-based polymer or the final product.

[0460] R 1c Preferably, it is a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms that contains 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms that contains a carbonyl group, or an alkyl group that contains a monovalent or divalent heterocyclic ring having 3 to 45 carbon atoms.

[0461] Examples of the surfactant (c) include the following surfactants. In each formula, A c is as described above.

[0462]

Chemical formula

[0463]

Chemical formula

[0464]

Chemical formula

[0465]

Chem.

[0466]

Chem.

[0467]

Chem.

[0468]

Chem.

[0469]

Chem.

[0470] The surfactant (c) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

[0472] In formula (d), R 1d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring etc. are mentioned. In R 1d a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0473] In the present specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the above heterocyclic ring.

[0474] R 1d As the above substituent that the above alkyl group may have, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0475] R 1d The above alkyl group preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by a halogen atom, up to 50% may be substituted by a halogen atom, and up to 25% may be substituted by a halogen atom. However, a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom is preferable. The above alkyl group preferably has no substituents.

[0476] R 1d Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms that may have a substituent. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents. Even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. Particularly preferably, it is a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably, it is a methyl group (-CH3).

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

[0478] R 2d and R 4d As the above substituents as R and R, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group are preferable, and a methyl group and an ethyl group are particularly preferable.

[0479] R 2d and R 4d The above alkyl group as R and R preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkyl group preferably has no substituents.

[0480] R 2d and R 4d As the above alkyl group as R and R, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0481] R 2d and R 4d As R and R, independently, H or a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is preferable, H or a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is still more preferable, and H is particularly preferable.

[0482] In formula (d), R 3dis an alkylene group having 1 to 10 carbon atoms which may have a substituent. R 3d , when there are a plurality of them, may be the same or different from each other.

[0483] The above alkylene group preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above alkylene group preferably has no substituents.

[0484] As the above alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent is preferable, a linear or branched alkylene group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkylene group having 1 to 10 carbon atoms that has no substituents is more preferable, and a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-) is even more preferable.

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

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

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

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

[0489] In formula (d), A d is -SO3X d or -COOX d (X d is H, a metal atom, NR 5d 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 5d is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different.). R 5d The organic group for R is preferably an alkyl group. R 5d is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferable. X d is a metal atom or NR 5d 4 (R 5d is as described above) may be. X d is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5d 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferable. Since it is more easily soluble in water, Na, K or NH4 is still more preferable. Since Na or NH4 is particularly preferable, and since it is easily removable, NH4 is most preferable. X dWhen it is NH4, the surfactant has excellent solubility in the aqueous medium, and it is difficult for metal components to remain in the TFE-based polymer or the final product.

[0490] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (however, excluding the carbonyl groups contained in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-). B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6d is more preferably H or a methyl group. * indicates the side bonded to A in the formula. d

[0491] L is preferably a single bond.

[0492] Examples of the surfactant (d) include, for example, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, ​(CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2SO3Na, CH3C(O)CH2CH2SO3Na, CH3C(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na and the like can be mentioned.

[0493] The surfactant (d) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

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

[0496] R 1e Examples of the substituent that the alkyl group as R may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group. A methyl group and an ethyl group are particularly preferable.

[0497] R 1e The alkyl group as R preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms. However, it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The alkyl group preferably has no substituents.

[0498] R 1e R is preferably a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms that may have a substituent. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents. Even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. A methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable, and a methyl group (-CH3) is most preferable.

[0499] Examples of the monovalent substituent include a group represented by the general formula: -Y e -R 6e a group represented by the general formula: -X e -A ea group represented by, -H, an optionally substituted C 1-20 alkyl group, -NH2, -NHR 9e (R 9e is an organic group (preferably an organic group not containing fluorine)), -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)) is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 10.

[0500] R 9e As, C 1-10 alkyl group or C 1-10 alkylcarbonyl group is preferred, C 1-4 alkyl group or C 1-4 alkylcarbonyl group is more preferred.

[0501] In the formula, X e is, in each occurrence, the same or different, a divalent linking group, or a bond. R 6e When does not contain any of a carbonyl group, an ester group, an amide group and a sulfonyl group, X e is preferably a divalent linking group containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group.

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

[0503] R 8e The organic group in is preferably an alkyl group. R 8eis H or C 1-10 The organic group of 1-4 is preferred, and the organic group of 1-4 is more preferred, and the alkyl group of

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

[0505] As the organic group in R 7e , an alkyl group is preferred. As R 7e , H or the organic group of 1-10 is preferred, and H or the organic group of 1-4 is more preferred, and H or the alkyl group of 1-4 is even more preferred. Examples of the above metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.

[0506] As M e , H, a metal atom or NR 7e 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7e 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

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

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

[0509] R 8e as the organic group in, an alkyl group is preferred. R 8e as, H or C 1-10 of an organic group is preferred, H or C 1-4 of an organic group is more preferred, H or C 1-4 of an alkyl group is even more preferred, and H is even more preferred.

[0510] In formula (e), R 6e is, in each occurrence, the same or different, an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms. The above R 6e of the organic group (preferably an organic group not containing fluorine) preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

[0511] R 6e of the alkyl group may contain 1 or 2 or more of at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms, but does not contain these groups at the terminal of the above alkyl group. The above R 6eThe alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, or may have 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0512] R 6e Examples include General formula: -R 10e -CO-R 11e a group represented by General formula: -R 10e -COO-R 11e a group represented by General formula: -R 11e a group represented by General formula: -R 10e -NR 8e CO-R 11e a group represented by, or General formula: -R 10e -CONR 8e -R 11e a group represented by (In the formula, R 8e represents H or an organic group (preferably an organic group not containing fluorine). R 10e is an alkylene group, and R 11e is an alkyl group which may have a substituent) is preferred. R 6e Examples of R 10e -CO-R 11e a group represented by are more preferred.

[0513] R 8e The organic group in is preferably an alkyl group. R 8e Examples of include H or an organic group of C 1-10 are preferred, H or an organic group of C 1-4 are more preferred, H or an alkyl group of C 1-4 are even more preferred, and H is even more preferred.

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

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

[0516] In formula (e), at least one of R 2e And R 5e Is a group represented by the general formula: -X e -A e And the A e Is -COOM e Is also one of the preferred embodiments.

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

[0518] General formula (e-1):

Chemical formula

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

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

[0521] General formula: -X e -A e As the group represented by, -COOM e , -R 12e COOM e , -SO3M e , -OSO3M e , -R 12e SO3M e , -R 12e OSO3M e , -OCO-R 12e -COOM e , -OCO-R 12e -SO3M e , -OCO-R 12e -OSO3M e , -COO-R 12e -COOM e , -COO-R 12e -SO3Me , -COO-R 12e -OSO3M e , -CONR 8e -R 12e -COOM e , -CONR 8e -R 12e -SO3M e , -CONR 8e -R 12e -OSO3M e , -NR 8e CO-R 12e -COOM e , -NR 8e CO-R 12e -SO3M e , -NR 8e CO-R 12e -OSO3M e , -OS(=O)2-R 12e -COOM e , -OS(=O)2-R 12e -SO3M e or -OS(=O)2-R 12e -OSO3M e (In the formula, R 8e and M e are as described above. R 12e is an alkylene group of C 1-10 .) is preferred. The alkylene group of the above R 12e may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, or may have 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

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

[0523] In the formula, R 4e and R 5e are, independently, preferably H or an alkyl group of C 1-4 . The above R 4e and R 5e alkyl groups may have up to 75% of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, up to 50% substituted by halogen atoms, or up to 25% substituted by halogen atoms, but are preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

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

[0525] R in the general formula (e-3) 2e is preferably H, OH, or an optionally substituted C 1-20 alkyl group, more preferably H, OH, or an unsubstituted C 1-20 alkyl group, and even more preferably H or OH. The above-mentioned R 2e alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, or may have 25% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

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

[0527] The above-mentioned specific hydrocarbon-based surfactant is preferably a carboxylic acid type hydrocarbon-based surfactant. The above-mentioned carboxylic acid type hydrocarbon-based surfactant is not limited as long as it has a carboxyl group (-COOH) or a group in which a hydrogen atom of the carboxyl group is substituted by an inorganic cation (for example, a metal atom, ammonium, etc.). For example, among the above-mentioned specific hydrocarbon-based surfactants, a hydrocarbon-based surfactant having a carboxyl group or a group in which a hydrogen atom of the carboxyl group is substituted by an inorganic cation can be used. The above-mentioned carboxylic acid type hydrocarbon-based surfactant preferably has a ratio of hydrogen atoms bonded to carbon atoms substituted by fluorine atoms of 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (not substituted by fluorine atoms at all).

[0528] As the carboxylic acid type hydrocarbon surfactant, preferably, among at least one selected from the group consisting of surfactant (c) represented by the above formula (c) and surfactant (d) represented by the above formula (d), those having a carboxyl group (-COOH) or a group in which a hydrogen atom of the carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.) are preferred.

[0529] It is also preferable that the specific hydrocarbon surfactant is a sulfonic acid type hydrocarbon surfactant. The sulfonic acid type hydrocarbon surfactant is not limited as long as it has a -SO3H group, -OSO3H group, or a group in which a hydrogen atom of these groups is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.). For example, among the specific hydrocarbon surfactants described above, a hydrocarbon surfactant having a -SO3H group, -OSO3H group, or a group in which a hydrogen atom of these groups is substituted with an inorganic cation can be used. The sulfonic acid type hydrocarbon surfactant preferably has a ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms of 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0530] The TFE-based polymer composition of the present disclosure can be efficiently produced by using at least one of the above specific hydrocarbon surfactants. Further, the TFE-based polymer composition of the present disclosure may be produced by using two or more of the above specific hydrocarbon surfactants at the same time, or a compound having other surfactant properties other than the above specific hydrocarbon surfactant may be used at the same time as long as it has volatility or may remain in a molded body made of a TFE-based polymer or the like.

[0531] As the compound having other surfactant properties, for example, those described in JP-T-2013-542308, JP-T-2013-542309, JP-T-2013-542310, etc. can be used.

[0532] Compounds having other surface activity properties may be surfactants having a hydrophilic portion and a hydrophobic portion on the same molecule, for example, hydrocarbon surfactants. These may be cationic, nonionic or anionic. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above compound is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0533] Cationic surfactants usually have a positively charged hydrophilic portion such as alkylated ammonium bromide and other alkylated ammonium halides, and a hydrophobic portion such as long-chain fatty acids. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above cationic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0534] Anionic surfactants usually have a hydrophilic portion such as carboxylate, sulfonate or sulfate, and a hydrophobic portion which is a long-chain hydrocarbon portion such as alkyl. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above anionic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0535] Nonionic surfactants usually do not contain a charged group and have a hydrophobic portion which is a long-chain hydrocarbon. The hydrophilic portion of the nonionic surfactant contains a water-soluble functional group such as a chain of ethylene ether derived from polymerization with ethylene oxide. It is preferable that the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the nonionic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0536] Examples of nonionic surfactants Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, glycerol ester, and derivatives thereof.

[0537] Specific examples of polyoxyethylene alkyl ether: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, etc.

[0538] Specific examples of polyoxyethylene alkyl phenyl ether: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, etc.

[0539] Specific examples of polyoxyethylene alkyl ester: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, etc.

[0540] Specific examples of sorbitan alkyl ester: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.

[0541] Specific examples of polyoxyethylene sorbitan alkyl ester: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, etc.

[0542] Specific examples of glycerol esters: glycerol monomyristate, glycerol monostearate, glycerol monooleate, etc.

[0543] Specific examples of the above derivatives: polyoxyethylene alkylamine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, etc.

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

[0545] Examples of nonionic surfactants include Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol (registered trademark) L series manufactured by Dow Chemical Company; Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)), Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10, etc.) manufactured by BASF.

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

[0547] Other compounds having surfactant properties include R-L-M (wherein R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when having 3 or more carbon atoms, may contain a monovalent or divalent heterocyclic ring or may form a ring; L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR5 4(R 5 may be the same or different, and is H or an organic group (preferably an organic group not containing fluorine), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an arylsulfonate. ) Also included are anionic surfactants represented by R 5 is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms. Specifically, CH3-(CH2) n -L-M (wherein n is an integer of 6 to 17. L and M are the same as above) are also included. A mixture in which R is an alkyl group having 12 to 16 carbon atoms and L-M is a sulfate or sodium dodecyl sulfate (SDS) can also be used. Other compounds having surfactant properties include R 6 (-L-M)2 (wherein R 6 is a linear or branched alkylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms which may have a substituent, and when having 3 or more carbon atoms, may contain a monovalent or divalent heterocyclic ring or may form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR 5 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent, R 5 is H or an organic group (preferably an organic group not containing fluorine), -ArSO3 - is an arylsulfonate. ) Also included are anionic surfactants represented by Other compounds having surfactant properties include R 7 (-L-M)3 (wherein R 7is a linear or branched alkylidine group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylidine group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - , and M is H, a metal atom, NR 5 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent, R 5 is H or an organic group (preferably an organic group not containing fluorine). -ArSO3 - is an aryl sulfonate. ) Also included are anionic surfactants represented by.

[0548] Examples of siloxane hydrocarbon surfactants include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of the siloxane surfactant includes a distinct hydrophobic part and a hydrophilic part. The hydrophobic part contains one or more dihydrocarbylsiloxane units, where the substituents on the silicone atoms are completely hydrocarbons. In the sense that when the carbon atoms of the hydrocarbyl group can be substituted by a halogen such as fluorine, they are completely substituted by hydrogen atoms, these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituents on the carbon atoms of the hydrocarbyl group are hydrogen. Preferably, the above siloxane surfactant has a ratio of hydrogen atoms bonded to carbon atoms substituted by fluorine atoms of 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted by fluorine atoms at all).

[0549] The siloxane hydrocarbon surfactant is also disclosed in U.S. Patent No. 6,841,616.

[0550] Examples of the siloxane-based anionic hydrocarbon surfactants include SilSense available from Noveon® Consumer Specialties, Lubrizol Advanced Materials, Inc. TM PE-100 silicone, SilSense TM CA-1 silicone, etc.

[0551] Examples of the anionic hydrocarbon surfactants also include sulfosuccinate surfactants such as Lankropol® K8300 manufactured by Akzo Nobel Surface Chemistry LLC. Examples of the sulfosuccinate surfactants include sodium diisodecyl sulfosuccinate, (Emulsogen® SB10 manufactured by Clariant), sodium diisotridecyl sulfosuccinate (Polirol® TR / LNA manufactured by Cesapinia Chemicals), etc.

[0552] Examples of the other compounds having surfactant properties include PolyFox® surfactants (PolyFox TM PF-156A, PolyFox TM PF-136A, etc.) manufactured by Omnova Solutions, Inc.

[0553] The other compounds having surfactant properties are preferably anionic hydrocarbon surfactants. As the anionic hydrocarbon surfactants, those described above can be adopted, and for example, the following hydrocarbon surfactants can be preferably adopted.

[0554] Examples of the above anionic hydrocarbon surfactants include, for example, the following formula (α): R 100 -COOM (α) (In the formula, R 100is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 101 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different. The compound (α) represented by ) is mentioned. The organic group of R 101 is preferably an alkyl group. R 101 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant properties, the number of carbon atoms of R 100 is preferably 2 or more, more preferably 3 or more. Also, from the viewpoint of water solubility, the number of carbon atoms of R 100 is preferably 29 or less, more preferably 23 or less. Examples of the metal atom of M include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K, or Li is preferred. As M, H, a metal atom, or NR 101 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 101 4 is more preferred, H, Na, K, Li, or NH4 is still more preferred, Na, K, or NH4 is still more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0555] Examples of the above compound (α) include an anionic surfactant represented by R 102 -COOM (wherein R 102 is a linear or branched alkyl group, alkenyl group, alkylene group, or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group, or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. M is the same as above.). Specifically, CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28. M is the same as above) is exemplified.

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

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

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

[0559] Examples of the compound (α) include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, ozbondic acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid, and salts thereof. In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof is preferable. Examples of the salt include those in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 11 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, but is not particularly limited.

[0560] Examples of the anionic hydrocarbon surfactant also include, for example, the following formula (β): R 100 -SO3M (β) (wherein R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 101 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.) The compound (β) represented by is also included. As the organic group of R 101 , an alkyl group is preferable. As R 101 , H or an organic group having 1 to 10 carbon atoms is preferable, H or an organic group having 1 to 4 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is still more preferable. From the viewpoint of surfactant performance, the number of carbon atoms of R 100 is preferably 2 or more, and more preferably 3 or more. Also, from the viewpoint of water solubility, the number of carbon atoms of R 100 is preferably 29 or less, and more preferably 23 or less. Examples of the metal atom of M include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferable. As M, H, a metal atom or NR 101 4 is preferable, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 101 4 is more preferable, H, Na, K, Li or NH4 is still more preferable, Na, K or NH4 is still more preferable, Na or NH4 is particularly preferable, and NH4 is most preferable.

[0561] Examples of the compound (β) include R 102 -SO3M (wherein R 102is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. M is the same as above.) Also included are anionic surfactants represented by Specifically, CH3-(CH2) n -SO3M (wherein n is an integer of 2 to 28. M is the same as above) is exemplified.

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

[0563] When the above alkyl group is linear, R 103It is preferably a C3-C29, more preferably a C5-C23. When the alkyl group is branched, the carbon number of R103 is preferably C5-C35, more preferably C11-C23. When the alkenyl group is linear, R 103 is preferably a C2-C29, more preferably a C9-C23. When the alkenyl group is branched, the carbon number of R103 is preferably C2-C29, more preferably C9-C23.

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

[0565] Examples of the compound (β) include sulfonic acids such as aliphatic, unsaturated aliphatic, aromatic, etc., sulfuric acid esters such as aliphatic, unsaturated aliphatic, aromatic, etc., and salts thereof. 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, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, butylnaphthalenesulfonic acid. Examples of the sulfuric acid ester include sodium alkyl sulfate, alpha-sulfo fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, alpha olefin sulfonate, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid. As the above compound (β), at least one selected from the group consisting of saturated aliphatic, aromatic sulfates, and salts thereof is particularly preferable, and at least one selected from the group consisting of sodium alkyl sulfate, alpha-sulfo fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, alpha olefin sulfonate, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid, and salts thereof is more preferable. As the above salt, 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, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and is not particularly limited.

[0566] As the above anionic hydrocarbon surfactant, the following formula (1-0A):

Chemical formula

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

[0568] In general formula (1-0A), R 2A and R 5A Any one of them is preferably a group represented by the general formula: -X A -A, and it is more preferable that R 2A is a group represented by the general formula: -X A -A.

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

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

[0571] Examples of the hydrocarbon surfactant represented by the general formula (1-0A) include glutaric acid or its salt, adipic acid or its salt, pimelic acid or its salt, suberic acid or its salt, azelaic acid or its salt, sebacic acid or its salt, and the like. Further, the aliphatic carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) may be a two-chain two-hydrophilic group type synthetic surfactant. For example, as a gemini type surfactant, Gemini SA-F (Chukyo Yushi Co., Ltd.), Gemsurf α142 (lauryl group having 12 carbon atoms), Gemsurf α102 (having 10 carbon atoms), Gemsurf α182 (having 14 carbon atoms), and the like can be mentioned.

[0572] Examples of the above anionic hydrocarbon surfactant include the following formula I: R-(XZ) n (I) (In the formula, R is a hydrophobic hydrocarbon moiety containing one or more saturated or unsaturated, acyclic or cyclic aliphatic groups. The percentage of the total of CH3 groups with respect to the total of CH3, CH2, and CH groups in one or more aliphatic groups is at least about 70%, and the hydrophobic moiety does not contain siloxane units. Each X may be the same or different and represents an ionic hydrophilic moiety. Each Z may be the same or different and represents one or more counterions of the ionic hydrophilic moiety. n is 1 to 3.) Compound I shown by is also included.

[0573] Compound I shows low reactivity with a polymerization initiator and / or a growing fluoropolymer radical in the emulsion polymerization of a fluoromonomer.

[0574] Compound I has the following formula:

Chem.

[0575] Compound I is the following formula II:

Chem.

[0576] As Compound II, for example, the following compounds are preferred.

Chem.

[0577] Compound I is the following formula III:

Chem.

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

[0579] The TFE-based polymer composition of the present disclosure can be obtained by a production method including a polymerization step of polymerizing only tetrafluoroethylene or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium having a pH of 4.0 or higher in the presence of a hydrocarbon-based surfactant and a polymerization initiator even when the above specific hydrocarbon-based surfactant is not used to obtain a TFE-based polymer. Conventionally, since a polymerization initiator showing acidity was used in the polymerization process for producing a TFE-based polymer, the pH of the aqueous medium used in the polymerization was less than 4.0. As a result of intensive studies by the present inventors, unexpectedly, it has been found that by setting the pH of the aqueous medium used in the polymerization to 4.0 or more, the polymerization stability is improved and a TFE-based polymer having a high molecular weight can be produced. The above production method polymerizes tetrafluoroethylene alone or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium having a pH of 4.0 or more. The pH may be 4.0 or more, preferably more than 4.0, more preferably 4.5 or more, still more preferably 5.0 or more, still more preferably 5.5 or more, particularly preferably 6.0 or more, particularly preferably 6.5 or more, particularly preferably 7.0 or more, particularly preferably 7.5 or more, and particularly preferably 8.0 or more. The upper limit value of the pH is not particularly limited, but may be, for example, 13.0 or less. From the viewpoint of corrosion of the polymerization tank, it is preferably 12.0 or less, more preferably 11.5 or less, and still more preferably 11.0 or less. The above pH can be measured with a pH meter.

[0580] In the above production method, the method for setting the pH of the aqueous medium to 4.0 or more is not limited. For example, the pH can be set to 4.0 or more by using an alkaline aqueous solution, using an aqueous dispersion showing alkalinity, or using a pH adjuster, but it is not particularly limited. Even when a polymerization initiator showing acidity when dissolved in an aqueous medium is used, the pH can be adjusted to 4.0 or more by further adding an alkaline compound such as sodium hydroxide. The alkaline compound may be a compound that dissolves in water and ionizes to generate OH - Any compound that can generate it is acceptable. Examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc., but it is not particularly limited. The above polymerization step may include a step of adding an alkaline compound to the aqueous medium.

[0581] In the above manufacturing method, the pH of the aqueous medium may be 4.0 or higher throughout all periods of the polymerization step. Also, the pH may be 4.0 or higher in the middle stage of the polymerization step, or the pH may be 4.0 or higher in the latter half of the polymerization step. Further, the pH may be 4.0 or higher in both the middle stage and the latter half of the polymerization step.

[0582] In the above polymerization step, from the start of polymerization, it is preferable that the pH of the aqueous medium is 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, particularly preferably 99% or more, most preferably 100%) of the period until the time when the polymer solid content concentration reaches 3% by mass (preferably 5% by mass, more preferably 8% by mass, still more preferably 10% by mass, even more preferably 15% by mass, particularly preferably 18% by mass, most preferably 20% by mass, especially preferably 25% by mass). In the above polymerization step, from the time when the polymer solid content concentration is 10% by mass (preferably 8% by mass, more preferably 5% by mass, still more preferably 3% by mass, even more preferably at the start of polymerization), it is preferable that the pH of the aqueous medium is 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, particularly preferably 99% or more, most preferably 100%) of the period until the time when the polymer solid content concentration reaches 15% by mass. In the above polymerization step, from the time when the polymer solid content concentration is 15% by mass, it is preferable that the pH of the aqueous medium is 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, particularly preferably 99% or more, most preferably 100%) of the period until the time when the polymer solid content concentration reaches 18% by mass (preferably 20% by mass, more preferably 25% by mass). The above polymerization step is preferably carried out with the pH of the aqueous medium being 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, more preferably 99% or more, 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, still more preferably 15% by mass, even more preferably 10% by mass, even more preferably 8% by mass, particularly preferably 5% by mass, more preferably 3% by mass, still more preferably the start of polymerization) until the end of polymerization. In any case, the pH of the above aqueous medium is preferably more than 4.0, more preferably 4.5 or higher, still more preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, especially preferably 6.5 or higher, more preferably 7.0 or higher, still more preferably 7.5 or higher, and even more preferably 8.0 or higher.

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

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

[0585] The TFE-based polymer composition of the present disclosure, even when not using the specific hydrocarbon surfactant described above, is obtained by polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant and a polymerization initiator. The hydrocarbon surfactant includes a salt of the hydrocarbon surfactant. In other words, at least a part of the anionic hydrocarbon surfactant in the polymerization step is in the form of a salt. As a result of intensive studies by the present inventors, surprisingly, it has been found that the stability of polymerization is improved by including a salt of the anionic hydrocarbon surfactant, and a TFE-based polymer having a large molecular weight can be produced. The anionic hydrocarbon surfactant will be described later. The fact that the anionic hydrocarbon surfactant includes a salt of the hydrocarbon surfactant can be confirmed by measuring the conductivity. In the above production method, it is preferable that the concentration of the salt of the anionic hydrocarbon surfactant in the anionic hydrocarbon surfactant is 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and especially preferably 95% by mass or more, based on the total mass of the anionic hydrocarbon surfactant. The ratio of the salt can be measured by the solution concentration and the conductivity. In the above production method, it is more preferable that the hydrocarbon surfactant is a carboxylic acid type hydrocarbon surfactant. The hydrocarbon surfactant does not contain fluorine. In the salt of the anionic hydrocarbon surfactant, the cation (excluding the hydrogen atom) that replaces the hydrogen atom of the acid is, for example, a metal atom, NR y 4(R yis each independently H or an organic group (preferably an organic group not containing fluorine), and may be the same or different, and is an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. The above R y 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. As the above cation in the salt of the anionic hydrocarbon surfactant, a metal atom or NR y 4 is preferred, and NR y 4 is more preferred, and NH4 is still more preferred. Since the conductivity changes greatly with the influence of temperature, a constant temperature bath is used to keep the sample liquid temperature at 25 °C, and the temperature of the cell of the pH meter is made the same, and then the conductivity is measured.

[0586] In the above production method, it is preferable that the polymerization step is carried out substantially in the absence of the hydrocarbon surfactant in the form of an organic acid. By carrying out the polymerization substantially in the absence of the hydrocarbon surfactant in the form of an organic acid, the stability of the polymerization is further improved, and a high molecular weight TFE-based polymer can be obtained. Substantially in the absence of the hydrocarbon surfactant in the form of an organic acid means that the concentration of the organic acid is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less based on the mass of the obtained aqueous dispersion. In this specification, "organic acid" means an organic compound showing acidity. Examples of the organic acid include carboxylic acids having a -COOH group and sulfonic acids having a -SO3H group, and carboxylic acids are preferred from the viewpoint of being easy to adjust the pH of an aqueous solution containing the organic acid. Also, the "form of an organic acid" means a form in which H of an acidic group (for example, -COOH group, -SO3H group, etc.) contained in the organic acid is not free. In the above production method, the hydrocarbon surfactant is an anionic hydrocarbon surfactant.

[0587] In the above polymerization step, the amount of the hydrocarbon surfactant at the start of polymerization is preferably more than 50 ppm with respect to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or more, more preferably 70 ppm or more, still more preferably 80 ppm or more, and even more preferably 100 ppm or more. The upper limit is not particularly limited, but for example, it is preferably 10,000 ppm, and more preferably 5,000 ppm. By the amount of the hydrocarbon surfactant at the start of polymerization being within the above range, an aqueous dispersion with a smaller average primary particle diameter and better stability can be obtained. It should be noted that the polymerization can be said to start when the gaseous TFE in the reactor becomes a TFE-based polymer and a pressure drop occurs in the reactor. U.S. Patent No. 3,391,099 (Punderson) discloses a dispersion polymerization of tetrafluoroethylene in an aqueous medium, which consists of two separate stages of the polymerization process: first, the formation of polymer nuclei as nucleation sites, and then a growth stage including the polymerization of established particles. Note that the polymerization usually starts when both the monomer to be polymerized and the polymerization initiator are filled into the reactor. In the present disclosure, an additive related to the formation of nucleation sites is used as a nucleating agent.

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

[0589] The hydrocarbon surfactant added in the above addition step is preferably 0.0001 to 10% by mass based on the aqueous medium. More preferably, it is 0.001% by mass or more, still more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more with respect to the aqueous medium. Also, with respect to the aqueous medium, it is more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

[0590] Since the polymerization stability is improved and a higher molecular weight TFE-based polymer can be obtained, the above composition preferably contains a hydrocarbon surfactant and is an aqueous solution having a pH of 5.0 or more. The pH of the above aqueous solution is more preferably 6.0 or more, still more preferably 6.5 or more, still more preferably 7.0 or more, particularly preferably 7.5 or more, and particularly preferably 8.0 or more. Also, the upper limit of the pH is not particularly limited, and it may be 12.0 or less, or may be 11.0 or less.

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

[0592] Examples of the carboxylic acid type hydrocarbon surfactant used in the above polymerization step and addition step include the above surfactant (e), the anionic surfactant represented by the above formula: R 6 (-L-M)2, and among the anionic surfactants represented by the above formula: R 7 (-L-M)3, those having a carboxyl group (-COOH) or a group in which a hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.), the above compound (α), the above surfactant (1-0A), and those obtained by subjecting these surfactants to radical treatment or oxidation treatment. It is preferably at least one selected from the group consisting of. The above carboxylic acid type hydrocarbon surfactant may be used alone or as a mixture of two or more. The above compound (α) includes not only the anionic hydrocarbon surfactant represented by the above formula: R 102 -COOM (wherein R 102 and M are the same as above), preferably the compound represented by formula (A1), but also the anionic surfactant represented by the above formula: R-L-M (wherein R, L and M are the same as above), the above surfactant (c) and the above surfactant (d), among which those having a carboxyl group (-COOH) or a group in which a hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.) are also included.

[0593] The above carboxylic acid type hydrocarbon surfactant is preferably the above compound (α), the compound represented by the above formula (A1), the compound in which A c is -COOX c in the above formula (c), the compound in which A d is -COOX d in the above formula (d), the compound in which A e is -COOM eIt is more preferable that it is at least one selected from the group consisting of a compound, a compound in which A is -COOM in the above formula (1-0A), and those obtained by subjecting these compounds to radical treatment or oxidation treatment. It is even more preferable that it is at least one selected from the group consisting of the compound represented by the above formula (A1) and those obtained by subjecting the compound to radical treatment or oxidation treatment. In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof, and those obtained by subjecting these compounds to radical treatment or oxidation treatment is preferable. Examples of the above salts include those in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 101 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, but is not particularly limited.

[0594] The above production method preferably polymerizes tetrafluoroethylene substantially in the absence of a fluorine-containing surfactant. In the above production method, "substantially in the absence of a fluorine-containing surfactant" means that the fluorine-containing surfactant is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, still more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, even more preferably 1 mass ppb or less, and particularly preferably less than 1 mass ppb with respect to the aqueous medium. "Substantially in the absence of a fluorine-containing surfactant" also means that there is no intentional addition of a fluorine-containing surfactant.

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

[0596] The fluorine-containing surfactant may also be a surfactant containing fluorine with the molecular weight of the anionic moiety being 1000 or less, preferably 800 or less. The "anionic moiety" means the part excluding the cation of the fluorine-containing surfactant. For example, in the case of F(CF2) n1 COOM represented by the following formula (I), it is the part of "F(CF2) n1 COO".

[0597] Specific examples of the fluorine-containing surfactant include those described in 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, U.S. Patent No. 3250808, U.S. Patent No. 3271341, Japanese Patent Application Laid-Open 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, International Publication No. 2013 / 189826, and the like.

[0598] Examples of the anionic fluorine-containing surfactant include compounds represented by the general formula (N 0 ) described above.

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

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

[0601] As the above radical scavenger, a compound having no restart ability after addition or chain transfer to free radicals in the polymerization system is used. Specifically, a compound having a function of easily causing a chain transfer reaction with a primary radical or a growing radical and then generating a stable radical that does not react with a monomer, or easily causing an addition reaction with a primary radical or a growing radical to generate a stable radical is used. Generally, what is called a chain transfer agent is characterized by its activity by a chain transfer constant and a restart efficiency. Among chain transfer agents, those with a restart efficiency of almost 0% are called radical scavengers. The above radical scavenger can also be, for example, a compound having a chain transfer constant with TFE at the polymerization temperature larger than the polymerization rate constant and a restart efficiency of substantially zero%. "The restart efficiency is substantially zero%" means that the generated radicals turn the radical scavenger into stable radicals. Preferably, it is a compound having a chain transfer constant (Cs) (= chain transfer rate constant (kc) / polymerization rate constant (kp)) with TFE at the polymerization temperature greater than 0.1. For the above compound, it is more preferable that the chain transfer constant (Cs) is 0.5 or more, further preferably 1.0 or more, still more preferably 5.0 or more, and particularly preferably 10 or more.

[0602] As the radical scavenger in the present disclosure, for example, at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl2) is preferable. Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m- or p-salicylic acid, gallic acid, naphthol, and the like. Examples of the unsubstituted phenol include o-, m- or p-nitrophenol, o-, m- or p-aminophenol, p-nitrosophenol, and the like. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, naphthoresorcinol, and the like. Examples of the aromatic amines include o-, m- or p-phenylenediamine, benzidine, and the like. Examples of the quinone compound include o-, m- or p-benzoquinone, 1,4-naphthoquinone, alizarin, and the like. Examples of the thiocyanate include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN), and the like. Among them, the aromatic hydroxy compound is preferable as the radical scavenger, the unsubstituted phenol or polyhydric phenol is more preferable, and hydroquinone is still more preferable.

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

[0604] As the decomposer of the polymerization initiator, any compound that can decompose the polymerization initiator used may be used. For example, at least one selected from the group consisting of sulfites, bisulfites, bromates, diimines, diimine salts, oxalic acid, oxalates, copper salts, and iron salts is preferable. 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. The addition amount of the decomposer of the polymerization initiator is added in the range of 25 to 300% by mass with respect to the amount of the oxidizing agent combined as the polymerization initiator (a redox initiator described later). Preferably, it is 25 to 150% by mass, and more preferably 50 to 100% by mass. From the viewpoint of reducing the standard specific gravity, the addition amount of the decomposer of the polymerization initiator is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration. A more preferable lower limit is 5% (molar basis), more preferably 8% (molar basis), still more preferably 10% (molar basis), still more preferably 13% (molar basis), and even more preferably 15% (molar basis). A more preferable upper limit is 400% (molar basis), more preferably 300% (molar basis), even more preferably 200% (molar basis), and particularly preferably 100% (molar basis).

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

[0606] The addition step may be a step of continuously adding at least one selected from the group consisting of a radical scavenger and a decomposer of the polymerization initiator. The continuous addition of at least one selected from the group consisting of a radical scavenger and a decomposer of a polymerization initiator means, for example, adding at least one selected from the group consisting of a radical scavenger and a decomposer of a polymerization initiator not all at once, but over time, without interruption or in portions.

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

[0608] As the above nucleating agent, for example, it is preferably at least one selected from the group consisting of fluoropolyethers, nonionic su...

Claims

1. A tetrafluoroethylene-based polymer composition for use in a binder for an electrochemical device, the tetrafluoroethylene-based polymer composition having an average particle size of 1 μm or more and 300 μm or less and an average aspect ratio of 2.0 or less.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

20. 7. The binder for electrochemical devices according to claim 5 or 6, which is a binder for lithium ion secondary batteries.

21. A tetrafluoroethylene-based polymer composition for use in a binder for electrochemical devices, the tetrafluoroethylene-based polymer composition having an average particle size of 1 μm or more and 300 μm or less, and a ratio of particles having an aspect ratio of 3.0 or more of 15% or less.

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

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

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

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

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

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

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

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

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

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

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

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