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

Abstract

Provided are: a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device that makes it possible to improve the cycle characteristics of the electrochemical device and suppress gas generation; and a binder for an electrochemical device, an electrode mixture, an electrode, and a secondary battery, in which the aforementioned composition is used. The tetrafluoroethylene-based polymer composition for use in a binder for an electrochemical device contains a tetrafluoroethylene-based polymer in which the number of carboxy groups is 4 or less per 106 of the main chain carbon atoms.

Description

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

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

[0002] Secondary batteries such as lithium-ion secondary batteries are used in small, portable electrical and electronic devices such as notebook computers, mobile phones, smartphones, tablet computers, and ultrabooks because of their high voltage, high energy density, low self-discharge, low memory effect, and the ability to be ultra-lightweight, and are also being put into practical use as a wide range of power sources, including on-board power sources for driving automobiles and large-scale stationary power sources. Demand is now being placed on secondary batteries to achieve even higher energy densities, and further improvements in their battery characteristics are being sought.

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

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

[0005] Patent Documents 7 and 8 describe composite binders of polytetrafluoroethylene and polyvinylidene fluoride or the like.

[0006] Patent Publication No. 2017-517862 International Publication No. 2021 / 181887 International Publication No. 2021 / 192541 International Publication No. 2022 / 138942 International Publication No. 2022 / 138939 International Publication No. 2023 / 054713 International Publication No. 2023 / 286787 International Publication No. 2022 / 234227

[0007] An object of the present disclosure is to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device, which can improve the cycle characteristics of an electrochemical device and suppress gas generation, as well as a binder for an electrochemical device, an electrode mixture, an electrode, and a secondary battery using the same.

[0008] The present disclosure (1) is a tetrafluoroethylene-based polymer composition used in a binder for an electrochemical device, wherein the number of carboxy groups is 10 and the number of main chain carbon atoms is 10. ６ The tetrafluoroethylene-based polymer composition contains 4 or less tetrafluoroethylene-based polymers per particle.

[0009] The present disclosure (2) is directed to a tetrafluoroethylene-based polymer having a main chain carbon number of 10 and a carboxyl group number of 10. ６ The tetrafluoroethylene-based polymer composition according to the present disclosure (1) has two or less per unit area.

[0010] The present disclosure (3) is the tetrafluoroethylene polymer composition according to the present disclosure (1) or (2), which has a standard specific gravity of 2.130 or more and 2.180 or less.

[0011] The present disclosure (4) is a tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (3), which is used as a binder for lithium-ion secondary batteries and is in the form of a powder.

[0012] The present disclosure (5) is a binder for electrochemical devices consisting essentially of a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition has a carboxyl group number of 10 or more and a main chain carbon number of 10 or more. ６ The binder for electrochemical devices contains a tetrafluoroethylene-based polymer having four or less units per particle.

[0013] The present disclosure (6) is a method for manufacturing a tetrafluoroethylene-based polymer having a main chain carbon number of 10 and a carboxyl group number of 10. ６ The binder for electrochemical devices according to the present disclosure (5), wherein the number of particles per particle is two or less.

[0014] The present disclosure (7) is the binder for electrochemical devices according to the present disclosure (5) or (6), wherein the tetrafluoroethylene polymer composition has an endothermic peak temperature of 333°C or higher and 350°C or lower.

[0015] The present disclosure (8) is the binder for electrochemical devices according to any one of the present disclosures (5) to (7), wherein the tetrafluoroethylene-based polymer composition has fibrillating ability.

[0016] The present disclosure (9) is the binder for electrochemical devices according to any one of the present disclosures (5) to (8), wherein the standard specific gravity of the tetrafluoroethylene-based polymer composition is 2.280 or less.

[0017] The present disclosure (10) is the binder for electrochemical devices according to any one of the present disclosures (5) to (9), wherein the standard specific gravity of the tetrafluoroethylene polymer composition is 2.130 or more and 2.180 or less.

[0018] The present disclosure (11) is a binder for lithium ion secondary batteries, and is the binder for electrochemical devices according to any one of the present disclosures (5) to (10) in the form of powder.

[0019] The present disclosure (12) is an electrode mixture comprising the tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (4) or the binder for electrochemical devices according to any one of the present disclosures (5) to (11), and an electrode active material.

[0020] The present disclosure (13) is the electrode mixture according to the present disclosure (12) in the form of a sheet.

[0021] The present disclosure (14) is an electrode comprising the tetrafluoroethylene-based polymer composition according to any one of the present disclosures (1) to (4) or the binder for electrochemical devices according to any one of the present disclosures (5) to (11), an electrode active material, and a current collector.

[0022] The present disclosure (15) is a secondary battery comprising the electrode according to the present disclosure (14).

[0023] According to the present disclosure, it is possible to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device that can improve the cycle characteristics of an electrochemical device and suppress gas generation, as well as a binder for an electrochemical device, an electrode mixture, an electrode, and a secondary battery that use the same.

[0024] In the present disclosure, the term "organic group" refers to a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. The organic group is preferably an alkyl group which may have one or more substituents.

[0025] The present disclosure will be specifically described below.

[0026] The present disclosure provides a tetrafluoroethylene (TFE)-based polymer composition for use in a binder for an electrochemical device, the TFE-based polymer composition having a main chain carbon number of 10 and a carboxyl group number of 10. ６ The present invention provides a TFE-based polymer composition comprising no more than four TFE-based polymers per molecule.

[0027] The TFE-based polymer composition of the present disclosure, when used as a binder for electrochemical devices, can improve the cycle characteristics of the electrochemical device and suppress gas generation. It can also improve the ionic conductivity of the electrochemical device. Furthermore, the amount of hydrogen fluoride eluted is small, which can suppress oxidation of metal components (such as outer cans) of the electrochemical device and suppress deterioration of electrical properties. It can also obtain a composite sheet with excellent strength and flexibility. The TFE-based polymer composition of the present disclosure can also be used in a dry process, eliminating the need to use a large amount of a dispersion medium such as water or an organic solvent. This allows for a wide selection of electrode active materials and solid electrolytes to be combined, which is advantageous in terms of the production process. It can also reduce the steps and costs associated with the use of a dispersion medium. Furthermore, the TFE-based polymer composition of the present disclosure has excellent binding strength with active materials and electrolytes, allowing for a reduction in the amount used.

[0028] The TFE polymer in the TFE polymer composition of the present disclosure has a carboxyl group number of 10 carbon atoms in the main chain. ６ The number of carboxy groups per unit is four or less, but from the viewpoint of further improving the battery characteristics (cycle characteristics, amount of gas generated, ionic conductivity, etc.), the number of carboxy groups is preferably three or less, more preferably two or less, even more preferably one or less, and particularly preferably zero.

[0029] The TFE-based polymer in the TFE-based polymer composition of the present disclosure has a sulfonic acid group number of 10 or more and a main chain carbon number of 10 or more, in terms of further improving battery characteristics. ６Preferably, there are 4 or less per molecule, more preferably 3 or less, even more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0.

[0030] The TFE-based polymer in the TFE-based polymer composition of the present disclosure has a main chain carbon number of 10 or more, and the number of oxygen-containing polar groups is 10 or more, so that the battery characteristics are further improved. ６ Preferably, there are 4 or less per molecule, more preferably 3 or less, even more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0.

[0031] Examples of the oxygen-containing polar group include a carbonyl group-containing group, an epoxy group, an oxetanyl group, and —SO ３ X ａ , -SO ２ X ａ , -OSO ２ X ａ , -PO ３ X ａ , and -OX ａ (In the formula, X ａ is —H, a metal atom, —NR １ ４ , an imidazolium group which may have a substituent, a pyridinium group which may have a substituent, a phosphonium group which may have a substituent, an alkyl group, or a nitrile group. １ is H or an organic group. Examples of the carbonyl group-containing group include -COOX ａ , -OCOX ａ (In the formula, X ａ is the same as above.), carbonate group, haloformyl group, acid anhydride residue, isocyanate group. The total number of these functional groups is preferably within the above-mentioned range.

[0032] X ａ is —H, a metal atom, —NR １ ４ , an imidazolium group which may have a substituent, a pyridinium group which may have a substituent, a phosphonium group which may have a substituent, an alkyl group, or a nitrile group. ａThe metal atom in the formula (I) includes monovalent and divalent metal atoms, such as alkali metals (group 1) and alkaline earth metals (group 2), and specific examples thereof include Na, K, and Li. １ may be the same or different. １ 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. ａ The number of carbon atoms in the alkyl group in X is preferably 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The alkyl group may be linear or cyclic. When the alkyl group is cyclic, it corresponds to a cycloalkyl group. ａ is —H, an alkali metal atom, NH ４ , an alkyl group, or a nitrile group, and —H, an alkali metal atom, NH ４ or an alkyl group, and more preferably —H, an alkali metal atom, or NH ４ It is more preferable that:

[0033] The identification and number of each functional group can be measured by infrared spectroscopy. Specifically, the number of functional groups is measured by the following method. First, a TFE-based polymer is melted at 330 to 340°C for 30 minutes and compression molded to produce a film with a thickness of 0.25 to 0.3 mm. This film is analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum of the TFE-based polymer, and a difference spectrum with a base spectrum in which the polymer is completely fluorinated and no functional groups are present is obtained. From the absorption peaks of specific functional groups that appear in this difference spectrum, the number of carbon atoms in the TFE-based polymer (1 x 10) can be calculated according to the following formula (A): ６ The number of functional groups per particle, N, is calculated as follows: N = I x K / t (A), where I is absorbance, K is correction coefficient, and t is film thickness (mm).

[0034] For reference, the absorption frequencies, molar absorption coefficients, and correction coefficients for the functional groups in this specification are shown in Table 1. The molar absorption coefficients were determined from FT-IR measurement data of low molecular weight model compounds.

[0035]

[0036] In addition, -CH ２ COF, -CH ２ COOH, -CH ２ COOCH ３ , -CH ２ CONH ２ The absorption frequencies of -COF, -COOHfree, -COOHbonded, and -COOCH are shown in the table. ３ , -CONH ２ absorption frequency from tens of Kaiser (cm －１ Therefore, for example, the number of functional groups of -COF is -CF ２ Absorption frequency due to COF: 1883 cm －１ The number of functional groups determined from the absorption peak of -CH ２ Absorption frequency due to COF: 1840 cm －１ The number of functional groups is the sum of the number of functional groups determined from the absorption peaks of the compounds.

[0037] Above-mentioned TFE polymer can be high molecular weight TFE polymer, can be low molecular weight TFE polymer, and can be their mixture.When the mixture of high molecular weight TFE polymer and low molecular weight TFE polymer, it is preferred that high molecular weight TFE polymer is the main component.In the mixture, the endothermic peak temperature has endothermic peak in the region (A) that is 324 ℃ or more and less than 333 ℃, and in the region (B) that is 333 ℃ or more and 350 ℃ or less, and the intensity ratio that is represented by the endothermic peak intensity of the region (A) / the endothermic peak intensity of the region (B) is 0.05 or more and 3.50 or less.

[0038] The high molecular weight TFE polymer preferably has a standard specific gravity (SSG) of 2.280 or less, more preferably 2.250 or less, even more preferably 2.220 or less, even more preferably 2.200 or less, even more preferably 2.190 or less, especially preferably 2.180 or less, and particularly preferably 2.170 or less. The SSG is also preferably 2.130 or more. The SSG is measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895 89.

[0039] The endothermic peak temperature of the high molecular weight TFE polymer is preferably 333° C. or higher and 350° C. or lower, more preferably 336° C. or higher, more preferably 348° C. or lower, and even more preferably 346° C. or lower. The endothermic peak temperature of the TFE polymer is the temperature corresponding to the minimum point in the heat of fusion curve obtained by carrying out differential scanning calorimetry (DSC) at a heating rate of 10° C. / min on a TFE polymer that has no history of being heated to a temperature of 300° C. or higher. When there are two or more minimum points in one melting peak, each of them is regarded as the endothermic peak temperature.

[0040] Preferably, above-mentioned high molecular weight TFE polymer is non-melt processable.In this specification, non-melt processable means that melt flow rate (MFR) is less than 0.25g / 10min, preferably less than 0.10g / 10min, more preferably 0.05g / 10min or less, even more preferably 0.01g / 10min or less.Above-mentioned MFR is the value (g / 10min) of the polymer mass that flows out per 10 minutes by using a melt indexer at 372 ℃ and 5kg load, and from a nozzle with an inner diameter of 2.095mm and a length of 8mm according to ASTM D1238.

[0041] The low-molecular-weight TFE polymer has a melt viscosity (complex viscosity) of 1.0×10 at 380° C. １ ~1.0 x 10 ７ The melt viscosity is preferably 1.0×10 Pa·s. ２ Pa s or more is more preferable, and 1.5 × 10３ It is more preferable that the viscosity is 7.0×10 Pa s or more. ３ It is particularly preferable that the viscosity is 7.0×10 Pa s or more. ５ Pa s or less is more preferable, and 3.0 × 10 ５ It is more preferable that the viscosity is 1.0×10 Pa s or less. ５ The melt viscosity is particularly preferably not more than Pa s. The melt viscosity is a value measured in accordance with ASTM D 1238 using a flow tester (manufactured by Shimadzu Corporation) and a 2φ-8L die, with a 2 g sample preheated at 380°C for 5 minutes being held at the above temperature under a load of 0.7 MPa.

[0042] The low-molecular-weight TFE polymer preferably has an endothermic peak temperature of 324°C or higher but lower than 333°C, more preferably 326°C or higher, and more preferably lower than 330°C.

[0043] Preferably, above-mentioned low molecular weight TFE polymer is melt processable.In this specification, melt processable means that melt flow rate (MFR) is 0.25g / 10min or more, preferably 0.50g / 10min or more, more preferably 1.00g / 10min or more.Above-mentioned MFR can be 100g / 10min or less, preferably 80g / 10min or less.

[0044] The TFE-based polymer may be a TFE homopolymer, or may be a TFE copolymer comprising a polymerized unit (TFE unit) based on TFE and a polymerized unit (modified monomer unit) based on a modified monomer copolymerizable with TFE.The TFE-based polymer may be polytetrafluoroethylene (PTFE).The PTFE includes a TFE homopolymer and a modified PTFE comprising 99.0% by mass or more of TFE unit and 1.0% by mass or less of modified monomer unit.In view of further improving battery performance, the TFE-based polymer is preferably PTFE, and more preferably modified PTFE.In addition, in the present disclosure, the TFE homopolymer refers to a polymer in which the content of modified monomer unit relative to the total polymerized unit is less than 0.0001% by mass.

[0045] The content of the modified monomer unit is preferably in the range of 0.0001 to 10% by mass relative to the total polymerized units, in order to further improve the battery characteristics. The lower limit of the content of the modified monomer unit is more preferably 0.001% by mass, even more preferably 0.010% by mass, even more preferably 0.015% by mass, and particularly preferably 0.020% by mass. The upper limit of the content of the modified monomer unit is preferably 5.0% by mass, more preferably 3.0% by mass, even more preferably 1.0% by mass, even more preferably 0.80% by mass, even more preferably 0.60% by mass, even more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, even more preferably 0.20% by mass, and particularly preferably 0.10% by mass. In this specification, the modified monomer unit refers to a portion of the molecular structure of the TFE-based polymer that is derived from the modified monomer.

[0046] The content of each of the above-mentioned polymerized units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0047] As the above-mentioned modified monomer, as long as it can be copolymerized with TFE, there is no particular limitation, for example, can be listed perfluoroolefin such as hexafluoropropylene (HFP); trifluoroethylene, vinylidene fluoride (VDF) etc. hydrogen-containing fluoroolefin; perhaloolefin such as chlorotrifluoroethylene (CTFE); perfluorovinyl ether; perfluoroallyl ether; (perfluoroalkyl) ethylene, ethylene, the monomer with polar group etc. In addition, the modified monomer used can be one kind or multiple kinds.

[0048] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (A): CF ２ =CF-ORf １ (A) (wherein, Rf １represents a perfluoroorganic group. ) and perfluorounsaturated compounds represented by the following formula: In this specification, the "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0049] The perfluorovinyl ether may be, for example, a compound represented by the general formula (A) in which Rf １ is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0050] Examples of the perfluoroalkyl group in the PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0051] The perfluorovinyl ether further includes a compound represented by the general formula (A) below, wherein Rf １ is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf １ is of the following formula:

[0052]

[0053] (wherein m represents 0 or an integer of 1 to 4), Rf １ is of the following formula:

[0054]

[0055] (wherein n represents an integer of 1 to 4).

[0056] The (perfluoroalkyl)ethylene [PFAE] is not particularly limited, and examples thereof include (perfluorobutyl)ethylene [PFBE] and (perfluorohexyl)ethylene.

[0057] Examples of perfluoroallyl ethers include those represented by the general formula (B): CF ２ =CF-CF ２ -ORf２ (B) (wherein, Rf ２ represents a perfluoroorganic group.

[0058] 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. ２ =CF-CF ２ -O-CF ３ , C.F. ２ =CF-CF ２ -O-C ２ F ５ , C.F. ２ =CF-CF ２ -O-C ３ F ７ , and CF ２ =CF-CF ２ -O-C ４ F ９ At least one selected from the group consisting of CF ２ =CF-CF ２ -O-C ２ F ５ , C.F. ２ =CF-CF ２ -O-C ３ F ７ , and CF ２ =CF-CF ２ -O-C ４ F ９ More preferably, at least one selected from the group consisting of CF ２ =CF-CF ２ -O-CF ２ CF ２ CF ３ is more preferred.

[0059] The 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. ４is F, Cl, Rf or O-Rf, and Rf is a perfluoroorganic group.

[0060] Rf in general formula (i) is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0061] The polar group-containing monomer may be a fluorine-free monomer or a fluorine-containing monomer.

[0062] Examples of the fluorine-free monomer include hydroxyl group-containing fluorine-free monomers such as hydroxyalkyl vinyl ethers, such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; carboxyl group-containing fluorine-free monomers, such as acrylic acid, methacrylic acid, itaconic acid, succinic acid, fumaric acid, crotonic acid, maleic acid, citraconic acid, undecylenic acid, and acetylenedicarboxylic acid; itaconic anhydride (hereinafter also referred to as "IAH"), citraconic anhydride (hereinafter also referred to as "CAH"), 5-norbornene-2, Examples of suitable monomers include 3-dicarboxylic acid anhydride (hereinafter also referred to as "NAH"), succinic anhydride, fumaric anhydride, maleic anhydride, and other fluorine-containing monomers having an acid anhydride residue; fluorine-containing monomers having a sulfo group such as vinyl sulfonic acid; fluorine-containing monomers having an epoxy group (glycidyl group) such as glycidyl vinyl ether and glycidyl allyl ether; fluorine-containing monomers having an amino group such as aminoalkyl vinyl ether and aminoalkyl allyl ether; fluorine-containing monomers having an amide group such as (meth)acrylamide and methylolacrylamide; and fluorine-containing monomers having a nitrile group such as acrylonitrile and methacrylonitrile. Among these, preferred are fluorine-containing monomers having a carboxy group and fluorine-containing monomers having an acid anhydride residue, more preferred are fluorine-containing monomers having an acid anhydride residue, and even more preferred are cyclic fluorine-containing monomers having an acid anhydride residue.

[0063] The polar group-containing monomer 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)").

[0064] The hydrophilic group in the modified monomer (A) is, for example, —NH ２ , -PO ３ M, -OPO ３ M, -SO ３ M, -OSO ３ M, -COOM (in each formula, M is H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring.) Among the above hydrophilic groups, -SO ３ M or -COOM is preferred. ７ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ More preferred are organic groups represented by the formula: １－４ The metal atom is preferably a monovalent or divalent metal atom, such as an alkali metal (Group 1) or an alkaline earth metal (Group 2), and more preferably Na, K, or Li.

[0065] Examples of the "functional group capable of reacting by radical polymerization" in the modifying monomer (A) include groups having an ethylenically unsaturated bond, such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond is a group represented by the following formula: CX ｅ X ｇ =CX ｆ R- (wherein, X ｅ , X ｆ and X ｇ are each independently F, Cl, H, or CF ３ , C.F. ２ H, C.F.H. ２ , or CH ３ and R is a linking group. The linking group of R can be represented by the formula: ａPreferably, the linking group is -CH=CH ２ , -CF=CH ２、 -CH=CF ２、 -CF = CF ２ , -CH ２ -CH=CH ２ , -CF ２ -CF=CH ２ , -CF ２ -CF = CF ２ , -(C=O)-CH=CH ２ , -(C=O)-CF=CH ２ , -(C=O)-CH=CF ２ , -(C=O)-CF=CF ２ , -(C=O)-C(CH ３ ) = CH ２ , -(C=O)-C(CF ３ ) = CH ２ , -(C=O)-C(CH ３ ) = CF ２ , -(C=O)-C(CF ３ ) = CF ２ , —O—CH ２ -CH=CH ２ , —O—CF ２ -CF=CH ２ , —O—CH ２ -CH=CF ２ , —O—CF ２ -CF = CF ２ Examples of groups having an unsaturated bond include the following.

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

[0067] The modifying monomer (A) may be used alone or in combination of two or more.

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

[0069] The modifying monomer (A) is preferably at least one selected from the group consisting of compounds represented by the following formulas (4a) to (4e): CF ２ =CF-(CF ２ ) ｎ１ -Y ３ (4a) (wherein n1 represents an integer of 1 to 10, and Y ３ is -SO ３ M １ or -COOM １ represents M １ , H, NH ４ or an alkali metal.) CF ２ =CF-(CF ２ C (CF ３ ) F) ｎ２ -Y ３ (4b) (wherein n2 represents an integer of 1 to 5, and Y ３ is the same as the definition above.) CF ２ =CF-O-(CFX １ ) ｎ３ -Y ３ (4c) (wherein, X １ is F or CF ３ n3 represents an integer of 1 to 10; Y ３ is the same as the definition above.) CF ２ =CF-O-(CF ２ CFX １ O) ｎ４ -CF ２ CF ２ -Y ３ (4d) (wherein n4 represents an integer of 1 to 10, and Y ３ and X １ is the same as the above definition.) CX ２ ２ =CFCF ２ -O-(CF(CF ３ )CF ２ O) ｎ５ -CF (CF ３ )-Y ３ (4e) (In the formula, each ２ are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, Y ３ is the same as defined above.) Examples of the alkali metal include Na and K.

[0070] In the formula (4a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. ３ is advantageous in that it can provide adequate water solubility and surface activity. １ Preferably, M １ is preferred because it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved. ４ It is preferable that:

[0071] Examples of the perfluorovinyl alkyl compound represented by the formula (4a) include CF ２ =CFCF ２ COOM １ (In the formula, M １ is the same as the definition above.

[0072] In the formula (4b), n2 is preferably an integer of 3 or less from the viewpoint of emulsifying ability, and Y ３ is preferred in that it provides adequate water solubility and surface activity. １ Preferably, M １ is preferred because it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved. ４ It is preferable that:

[0073] In the formula (4c), n3 is preferably an integer of 5 or less in terms of water solubility, and Y ３ is preferred in that it provides adequate water solubility and surface activity. １ It is preferable that the above M １ is H or NH in that dispersion stability is improved. ４ It is preferable that:

[0074] In the formula (4d), the X １ In terms of surfactant activity, -CF ３ In terms of water solubility, n4 is preferably an integer of 5 or less, and Y ３ COOM has the advantage of providing adequate water solubility and surface activity. １ It is preferable that the above M １ is H or NH ４It is preferable that:

[0075] Examples of the perfluorovinyl ether compound represented by the formula (4d) include CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ COOM １ (In the formula, M １ , H, NH ４ or an alkali metal.

[0076] In the formula (4e), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in terms of emulsifying ability. ３ COOM has the advantage of providing adequate water solubility and surface activity. １ It is preferable that the above M １ is preferred in that it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved. ４ It is preferable that:

[0077] Examples of the perfluorovinyl alkyl compound represented by the formula (4e) include CH ２ =CFCF ２ OCF (CF ３ ) COOM １ , C.H. ２ =CFCF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM1 (in the formula, M １ is the same as the definition above.

[0078] As the modified monomer, from the viewpoint of improving the stretchability, binding strength, and flexibility of the mixture sheet, at least one selected from the group consisting of HFP, PAVE, PFAE, and a monomer having a polar group is preferred, at least one selected from the group consisting of HFP, perfluoro(methyl vinyl ether) [PMVE], perfluoro(propyl vinyl ether) [PPVE], PFBE, a non-fluorinated monomer having an acid anhydride residue, and the modified monomer (A) is more preferred, at least one selected from the group consisting of HFP, PMVE, PPVE, a cyclic non-fluorinated monomer having an acid anhydride residue, and a compound represented by general formula (4e) is even more preferred, at least one selected from the group consisting of HFP and PPVE is even more preferred, and HFP is even more preferred.

[0079] The TFE polymer may have a core-shell structure. As the TFE polymer having a core-shell structure, for example, modified PTFE can be mentioned, which contains a core of high molecular weight PTFE in a particle and a shell of lower molecular weight PTFE or modified PTFE. As such modified PTFE, for example, PTFE described in JP-A-2005-527652 can be mentioned.

[0080] Above-mentioned TFE polymer can be the TFE polymer obtained by emulsion polymerization, can be the TFE polymer obtained by suspension polymerization, or can be the mixture thereof.In view of obtaining a composite sheet having excellent strength and flexibility, it is preferable to be the TFE polymer obtained by emulsion polymerization, and in view of further improving battery characteristics, it is more preferable to be the TFE polymer obtained by using fluorine-containing surfactant.

[0081] The content of the TFE polymer in the TFE polymer composition of the present disclosure may be 95.0% by mass or more, preferably 98.0% by mass or more, more preferably 99.0% by mass or more, even more preferably 99.5% by mass or more, particularly preferably 99.9% by mass or more, and most preferably 99.95% by mass or more, based on the TFE polymer composition.

[0082] The TFE-based polymer composition of the present disclosure is preferably substantially free of fluorine-containing compounds having hydrophilic groups.

[0083] Examples of the hydrophilic group include —SO ３ M ａ , -SO ２ M ａ , -OSO ２ M ａ , -PO ３ M ａ , -COOM ａ , -OCOM ａ , and -OM ａ (In the formula, M ａ is —H, a metal atom, —NR １ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R １ is H or an organic group. The hydrophilic group may be an ionic group, and is preferably an anionic group.

[0084] The fluorine-containing compound having a hydrophilic group can be exemplified by 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, more preferably 500 or less.The polymer particles obtained by polymerization in the presence of a fluorine-containing surfactant usually contain a fluorine-containing surfactant in addition to a TFE-based polymer.In this specification, the fluorine-containing surfactant is used during polymerization.The fluorine-containing compound having a molecular weight of 1000 or less may be a compound that is not added during polymerization, for example, a compound that is by-produced during polymerization.In addition, when the fluorine-containing compound having a molecular weight of 1000 or less contains an anionic moiety and a cationic moiety, it means a compound containing fluorine, the molecular weight of which of the anionic moiety is 1000 or less.The fluorine-containing compound having a molecular weight of 1000 or less does not include a TFE-based polymer.

[0085] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include surfactants containing fluorine in the anionic moiety with a molecular weight of 1000 or less (anionic fluorine-containing surfactants). The "anionic moiety" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF ２ ) ｎ１ In the case of COOM, "F(CF ２ ) ｎ１ This is the "COO" part.

[0086] The anionic fluorine-containing surfactant may be a surfactant represented by the general formula (N ０ ): X ｎ０ -Rf ｎ０ -Y ０ (N ０ ) (wherein, X ｎ０ is H, Cl or F. ｎ０ is a linear, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H atoms have been substituted with F, and the alkylene group may contain one or more ether bonds, and some of the H atoms may have been substituted with Cl. ０ is an anionic group.

[0087] Y ０ The anionic group is -COOM, -SO ２ M or -SO ３ M, -COOM, or -SO ３ M. M may be H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group. The metal atom includes alkali metals (Group 1), alkaline earth metals (Group 2), etc., such as Na, K, or Li. ７ As the group, H or C １－１０ and may be an organic group of the formula: １－４ and may be an organic group of the formula: １－４ M may be H, a metal atom, or an alkyl group of the formula NR ７４ and 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 NH ４ The above Rf ｎ０ may be one in which 50% or more of H is substituted with fluorine.

[0088] General formula (N ０ The compound represented by the general formula (N １ ): X ｎ０ -(CF ２ ) ｍ１ -Y ０ (N １ ) (wherein, X ｎ０ is H, Cl, and F, m1 is an integer from 3 to 15, and Y ０ is as defined above), a compound represented by the general formula (N ２ ): Rf ｎ１ -O-(CF(CF ３ )CF ２ O) ｍ２ CFX ｎ１ -Y ０ (N ２ ) (wherein, Rf ｎ１ is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, and X ｎ１ is F or CF ３ and Y ０ is as defined above), a compound represented by the general formula (N ３ ): Rf ｎ２ (CH ２ ) ｍ３ -(Rf ｎ３ ) ｑ -Y ０ (N ３ ) (wherein, Rf ｎ２ is a partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, and Rf ｎ３ is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y ０ is as defined above), a compound represented by the general formula (N４ ): Rf ｎ４ -O-(CY ｎ１ Y ｎ２ ) ｐ CF ２ -Y ０ (N ４ ) (wherein, Rf ｎ４ is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain an ether bond and / or a chlorine atom; 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 ): (In the formula, X ｎ２ , X ｎ３ and X ｎ４ Rf may be the same or different and are H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether linkage. ｎ５ is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms, which may contain an ether bond; L is a linking group; Y ０ is as defined above, where X ｎ２ , X ｎ３ , X ｎ４ and Rf ｎ５ wherein the total number of carbon atoms is 18 or less.

[0089] General formula (N ０More specifically, the compounds represented by the general formula (I) include perfluorocarboxylic acids (I), ω-H perfluorocarboxylic acids (II), general formula (III), perfluoroethercarboxylic acids (III), general formula (IV), perfluoroalkyl alkylene carboxylic acids (IV), general formula (V), perfluoroalkoxy fluorocarboxylic acids (V), general formula (VI), perfluoroalkyl sulfonic acids (VI), general formula (VII), ω-H perfluoro sulfonic acids (VII), general formula (VIII), perfluoroalkyl alkylene sulfonic acids (VIII), general formula (IX), alkyl alkylene carboxylic acids (IX), general formula (X), fluorocarboxylic acids (X), general formula (XI), alkoxy fluoro sulfonic acids (XI), general formula (XII), and compounds represented by the following general formula (XIII).

[0090] The perfluorocarboxylic acid (I) is represented by the general formula (I): F(CF ２ ) ｎ１ COOM (I) (wherein n1 is an integer of 3 to 14, and M is H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0091] The ω-H perfluorocarboxylic acid (II) is represented by the general formula (II): H(CF ２ ) ｎ２ COOM (II) (wherein n2 is an integer of 4 to 15, and M is as defined above).

[0092] The perfluoroethercarboxylic acid (III) is represented by the general formula (III): Rf １ -O-(CF(CF ３ )CF ２ O) ｎ３ CF (CF ３ ) COOM (III) (wherein, Rf１ is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.

[0093] The perfluoroalkyl alkylene carboxylic acid (IV) is represented by the general formula (IV): Rf ２ (CH ２ ) ｎ４ Rf ３ COOM (IV) (wherein, Rf ２ is a perfluoroalkyl group having 1 to 5 carbon atoms, and Rf ３ is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above.

[0094] The alkoxyfluorocarboxylic acid (V) is represented by the general formula (V): Rf ４ -O-CY １ Y ２ CF ２ -COOM (V) (wherein, Rf ４ is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain an ether bond and / or a chlorine atom; Y １ and Y ２ are the same or different and are H or F, and M is as defined above.

[0095] The perfluoroalkylsulfonic acid (VI) is represented by the general formula (VI): F(CF ２ ) ｎ５ SO ３ M (VI) (wherein n5 is an integer of 3 to 14, and M is as defined above).

[0096] The ω-H perfluorosulfonic acid (VII) is represented by the general formula (VII): H(CF ２ ) ｎ６ SO ３ M (VII) (wherein n6 is an integer of 4 to 14, and M is as defined above).

[0097] The perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the general formula (VIII): Rf ５ (CH ２ ) ｎ７ SO ３ M (VIII) (wherein, Rf ５ is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.

[0098] The alkyl alkylene carboxylic acid (IX) is represented by the general formula (IX): ６ (CH ２ ) ｎ８ COOM (IX) (wherein, Rf ６ is a linear or branched partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer from 1 to 3, and M is as defined above.

[0099] The fluorocarboxylic acid (X) is represented by the general formula (X): Rf ７ -O-Rf ８ -O-CF ２ -COOM (X) (wherein, Rf ７ is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether bond and / or a chlorine atom, and Rf ８ is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above.

[0100] The alkoxyfluorosulfonic acid (XI) is represented by the general formula (XI): Rf ９ -O-CY １ Y ２ CF ２ -SO ３ M (XI) (wherein, Rf ９ is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, and which is partially or completely fluorinated; Y １ and Y ２are the same or different and are H or F, and M is as defined above.

[0101] The compound (XII) is represented by the general formula (XII): (In the formula, X １ , X ２ and X ３ Rf may be the same or different and are H, F and linear or branched partially or fully fluorinated alkyl groups having 1 to 6 carbon atoms which may contain ether bonds; １０ is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y ０ is an anionic group. ０ is -COOM, -SO ２ M or -SO ３ M, and -SO ３ M or COOM (wherein M is as defined above). Examples of L include a single bond, a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms which may contain an ether bond.

[0102] The compound (XIII) has the following general formula (XIII): １１ -O-(CF ２ CF (CF ３ ) O) ｎ９ (CF ２ O) ｎ１０ CF ２ COOM (XIII) (wherein, Rf １１ is a fluoroalkyl group containing chlorine and having 1 to 5 carbon atoms, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above. ２ ClO(CF ２ CF (CF ３ ) O) ｎ９ (CF ２ O) ｎ１０ CF ２ COONH ４ (a mixture having an average molecular weight of 750, wherein n9 and n10 are defined above).

[0103] Thus, examples of the anionic fluorine-containing surfactant include carboxylic acid surfactants and sulfonic acid surfactants.

[0104] The fluorine-containing surfactant may be one type of fluorine-containing surfactant or a mixture containing two or more types of fluorine-containing surfactants.

[0105] Examples of the fluorine-containing surfactant include compounds represented by the following formula: F(CF ２ ) ７ COOM, F(CF ２ ) ５ COOM, H(CF ２ ) ６ COOM, H(CF ２ ) ７ COOM, C.F. ３ O (CF ２ ) ３ OCHFCF ２ COOM, C. ３ F ７ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM, C.F. ３ CF ２ CF ２ OCF (CF ３ ) COOM, C.F. ３ CF ２ OCF ２ CF ２ OCF ２ COOM, C. ２ F ５ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM, C.F. ３ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM, C.F. ２ ClCF ２ CF ２ OCF (CF ３ )CF ２ OCF ２ COOM, C.F. ２ ClCF２ CF ２ OCF ２ CF (CF ３ ) OCF ２ COOM, C.F. ２ ClCF(CF ３ ) OCF (CF ３ )CF ２ OCF ２ COOM, C.F. ２ ClCF(CF ３ ) OCF ２ CF (CF ３ ) OCF ２ COOM, and (In each formula, M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. ７ is H or an organic group.

[0106] In each of the above formulas, M is 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 NH ４ R ７ is H or C １－１０ and may be an organic group of the formula: １－４ and may be an organic group of the formula: １－４ The alkyl group may be:

[0107] The content of the above-mentioned anionic fluorine-containing surfactant is preferably 25 mass ppb or less, more preferably 20 mass ppb or less, even more preferably 15 mass ppb or less, even more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, even more preferably 1 mass ppb or less, even more preferably less than 1 mass ppb, and particularly preferably less than the lower limit of quantification, relative to the TFE-based polymer composition.The lower limit is not particularly limited, and may be the amount less than the lower limit of quantification.

[0108] The amount of the anionic fluorine-containing surfactant is measured by the following method. 1 g of sample is weighed, 10 g (12.6 ml) of methanol is added, and ultrasonic treatment is performed for 60 minutes to obtain an extract. The obtained extract is concentrated using a nitrogen purge as appropriate, and the fluorine-containing compounds in the concentrated extract are measured by LC / MS / MS. Molecular weight information is extracted from the obtained LC / MS spectrum, and a match with the structural formula of the candidate fluorine-containing compound is confirmed. Aqueous solutions with five or more levels of content of the standard substance are prepared, and LC / MS analysis is performed on the aqueous solutions with each content. The relationship between the content and the area area relative to that content is plotted, and a calibration curve is drawn. Using the calibration curve, the area area of ​​the LC / MS chromatogram of the fluorine-containing compound in the extract is converted to the content of the fluorine-containing compound. The lower limit of quantitation in this measurement method is 10 ppb by mass.

[0109] The fluorine-containing compound having a hydrophilic group with a molecular weight of 1,000 or less also includes a compound represented by the following general formula (1) (hereinafter also referred to as compound (1)). General formula (1): (H—(CF ２ ) ｍ－１ -COO) ｐ M １ (wherein m is 4 to 20. M １ represents H, a metal atom, NR ５ ４ (R ５ may be the same or different and are H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.

[0110] M １ Examples of the metal atom as R include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and specific examples include Na, K, and Li. ５ may be the same or different. ５ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0111] In general formula (1), m is preferably 6 or more, more preferably 8 or more, even more preferably 11 or more, even more preferably 13 or more, particularly preferably 15 or more, and is preferably 18 or less, more preferably 16 or less.

[0112] The content of compound (1) is preferably 25 mass ppb or less relative to the TFE-based polymer, more preferably 20 mass ppb or less, more preferably 15 mass ppb or less, more preferably 10 mass ppb or less, more preferably less than 10 mass ppb, more preferably 1 mass ppb or less, more preferably less than 1 mass ppb, particularly preferably less than the lower limit of quantification.The lower limit is not particularly limited, and can be the amount less than the lower limit of quantification.

[0113] The fluorine-containing compound having a hydrophilic group with a molecular weight of 1,000 or less also includes a compound represented by the following general formula (2) (hereinafter also referred to as compound (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.

[0114] M ２ Examples of the metal atom as R include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and specific examples include Na, K, and Li. ５ may be the same or different. ５ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0115] In general formula (2), n is preferably 6 or more, more preferably 8 or more, even more preferably 11 or more, even more preferably 13 or more, particularly preferably 15 or more, and is preferably 18 or less, more preferably 16 or less.

[0116] The content of compound (2) is preferably 25 mass ppb or less relative to the TFE-based polymer, more preferably 20 mass ppb or less, more preferably 15 mass ppb or less, more preferably 10 mass ppb or less, more preferably less than 10 mass ppb, more preferably 1 mass ppb or less, more preferably less than 1 mass ppb, particularly preferably less than the lower limit of quantification.The lower limit is not particularly limited, and can be the amount less than the lower limit of quantification.

[0117] The contents of compounds (1) and (2) are values ​​measured by liquid chromatography mass spectrometry as described in the Examples below.

[0118] The fluorine-containing compound having a hydrophilic group also includes a fluorine-containing compound having a hydrophilic group with a molecular weight of more than 1000, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight of more than 1000 g / mol.

[0119] Examples of the fluorine-containing compound having a hydrophilic group and a molecular weight of more than 1000 include polymer compounds having an ionic group. Note that the TFE-based polymer is not included in the polymer compounds.

[0120] The ionic group is preferably an anionic group, for example, a sulfate group, -COOM ａ (carboxylate group), phosphate group, -PO ３ M ａ (phosphonate group), —SO ３ M ａ (sulfonate group), —SO ２ M ａ (sulfinate group), —C(CF ３ ) ２ O.M. ａ (In each formula, M ａ is —H, a metal atom, —NR ２ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ is H or an organic group. ３ M ａ , -SO ２ M ａ , -PO ３ M ａ and -COOM ａ At least one selected from the group consisting of:

[0121] The content of the ionic group is preferably 0.80 meq / g or more, more preferably 1.20 meq / g or more, even more preferably 1.75 meq / g or more, even more preferably 2.00 meq / g or more, and particularly preferably 2.50 meq / g or more, relative to the 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 calculated from the composition of the polymer compound.

[0122] The polymer compound preferably contains fluorine atoms, and the proportion of hydrogen atoms bonded to carbon atoms in the polymer compound that are substituted with fluorine atoms is preferably 50% or more. The "proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms" is calculated as the proportion of fluorine atoms to the total number of hydrogen atoms bonded to carbon atoms and halogen atoms (including fluorine atoms) bonded to carbon atoms. The proportion of hydrogen atoms bonded to carbon atoms in the polymer compound that are substituted with fluorine atoms is not particularly limited, but is more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more, particularly preferably 95% or more, and most preferably 100%.

[0123] The polymer compound preferably has an ion exchange ratio (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the main chain of the polymer compound relative to the number of ionic groups. ２F) is not considered an ionic group for purposes of determining IXR. The IXR is preferably 0.5 or greater, more preferably 1 or greater, even more preferably 3 or greater, even more preferably 4 or greater, and especially preferably 5 or greater. Also, the IXR is preferably 43 or less, more preferably 33 or less, and even more preferably 23 or less. In the polymeric compound, the ionic groups are typically distributed along the polymer backbone. The polymeric compound preferably includes recurring side chains attached to the polymer backbone, the side chains carrying the ionic groups.

[0124] The polymer compound is preferably a water-soluble polymer compound. "Water-soluble" means the property of being easily dissolved or dispersed in an aqueous medium. For example, the particle size of a water-soluble polymer compound cannot be measured by dynamic light scattering (DLS), or the particle size is 5 nm or less. On the other hand, for example, the particle size of a water-insoluble polymer compound can be measured by dynamic light scattering (DLS) to be greater than 5 nm.

[0125] The number average molecular weight of the polymer compound is 0.1 × 10 ４ More than 0.15 × 10 is preferred. ４ More preferably, 0.2 × 10 ４ More preferably, 0.3 × 10 ４ More preferably, 0.5 × 10 ４ More preferably, 1.0 × 10 ４ More preferably, 2.0 × 10 ４ More preferably, 3.0 × 10 ４ More than 75.0×10 is most preferable. ４ Preferably, 50.0 x 10 ４ More preferably, 40.0 x 10 ４ More preferably, 30.0 x 10 ４ The following is particularly preferred: 20.0 x 10 ４ The following are particularly preferred:

[0126] The weight average molecular weight of the polymer compound is 0.1 × 10 ４ More than 0.2 × 10 is preferred. ４ More preferably, 0.4 × 10４ More preferably, 0.6 × 10 ４ More preferably, 1.0 × 10 ４ More preferably, 2.0 × 10 ４ More preferably, 5.0 x 10 ４ More than 150.0×10 is most preferable. ４ The following is preferred: 100.0 x 10 ４ More preferably, 80.0 x 10 ４ More preferably, 60.0 x 10 ４ The following is particularly preferred: 40.0 x 10 ４ The following are particularly preferred:

[0127] The number average molecular weight and weight average molecular weight are values ​​calculated by gel permeation chromatography (GPC) using monodisperse polystyrene or monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) as standards. Furthermore, when measurement by GPC is not possible, the number average molecular weight of the polymer compound can be determined from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0128] The polymer compound preferably contains substantially no fractions having a molecular weight of 1,000 or less, more preferably contains substantially no fractions having a molecular weight of less than 1,500, even more preferably contains substantially no fractions having a molecular weight of less than 2,000, and particularly preferably contains substantially no fractions having a molecular weight of less than 3,000. "Substantially no fractions" means that the content of the fractions relative to the polymer compound is 3.0% by mass or less. The content of the fractions relative to the polymer compound is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. The content of the fractions can be measured by gel permeation chromatography (GPC) or liquid chromatography-mass spectrometry (LC-MS).

[0129] It is preferable that the polymer compound is substantially free of fluorine-containing compounds having a molecular weight of 1000 or less. "Substantially free of fluorine-containing compounds" means that the amount of the fluorine-containing compounds is 25 mass ppb or less relative to the polymer compound. The amount of the fluorine-containing compounds is more preferably less than 25 mass ppb, even more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, even more preferably 5 mass ppb or less, even more preferably 3 mass ppb or less, even more preferably 1 mass ppb or less, and particularly preferably less than 1 mass ppb. The lower limit is not particularly limited and may be an amount below the detection limit. The fluorine-containing compounds having a molecular weight of 1000 or less and a method for quantifying them will be described later.

[0130] The polymer compound is preferably at least one selected from the group consisting of a polymer (I) containing a polymerized 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) (wherein, X １ and X ３ are each independently F, Cl, H or CF ３ and A ０ is an anionic group; X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more.) General formula (II): T Ｘ -X Ａ -R ＦＡ１ -R ＦＡ２ -X Ａ -T Ｘ '(II) (wherein, R ＦＡ１ is -Rf １ ｐ -R Ｆ -Oｑ - 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, and Rf １ and Rf ２ each independently represents a C optionally substituted by one or more fluorine atoms; １－６ each p is independently 0 or 1; each q is independently 0 or 1; X Ａ are each independently a single bond or a divalent to decavalent group, Ｘ and T Ｘ (i) each independently contains one or more of H, O, and Cl, and does not contain the anionic group; １ ~C ２４ (hydro)(fluoro)carbon groups, and (ii) at least one of the anionic groups described above. １ ~C ２４ (hydro)(fluoro)carbon groups.)

[0131] The polymer (I) is a polymer containing polymerized units (I) based on the monomer (I). The monomer (I) is represented by the following general formula (I): CX １ X ３ =CX ２ R (-CZ １ Z ２ -A ０ ) ｍ (I) (wherein, X １ and X ３ are each independently F, Cl, H or CF ３ and X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is an anionic group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more. ２as F, Cl, H or CF ３ In addition, Z １ and Z ２ As the ３ is preferred.

[0132] In the present disclosure, anionic groups include anionic groups such as sulfate groups, carboxylate groups, and acid groups such as —COOH, —COONH ４ The anionic group includes a functional group that provides an anionic group such as an acid-base group, such as a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group, a sulfinate group, or a —C(CF ３ ) ２ O.M. ａ (In the formula, M ａ is —H, a metal atom, —NR ２ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ is H or an organic group.

[0133] In the present disclosure, one or more types of monomers can be used as the monomer (I) represented by general formula (I).

[0134] R is a linking group. In the present disclosure, a "linking group" is an (m+1)-valent linking group, and when m is 1, it is a divalent linking group. The linking group may be a single bond and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. There is no upper limit, but it may be, for example, 100 or less, or 50 or less.

[0135] The linking group may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and may optionally contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may optionally contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate. The linking group may not contain carbon atoms but may be a catenary heteroatom such as oxygen, sulfur, or nitrogen.

[0136] m is an integer of 1 or more, preferably 1 or 2, and more preferably 1. When m is an integer of 2 or more, Z １ , Z ２ and A ０ may be the same or different. Next, a preferred structure when m is 1 in general formula (I) will be described.

[0137] R is preferably a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0138] It is also preferred that the polymer (I) is highly fluorinated. For example, the polymer (I) may contain phosphate group moieties (e.g., CH ２ OP (O) (OM ａ ) ２ ) and sulfate group moieties (e.g., CH ２ OS (O) ２ O.M. ａ anionic groups such as ０ ), it is preferred that 80% or more, 90% or more, 95% or more, or 100% of the C—H bonds in the polymer (I) are substituted with C—F bonds.

[0139] The monomer (I) and the polymer (I) contain an anionic group (A ０ ) except for the above, it is also preferable that the compound has a C—F bond and does not have a C—H bond. １ , X ２ , and X ３is preferably F, and R is a perfluoroalkylene group having one or more carbon atoms, and the perfluoroalkylene group may be either linear or branched, may be cyclic or acyclic, and may contain at least one catenary heteroatom. The number of carbon atoms in the perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0140] The monomer (I) and the polymer (I) may be partially fluorinated. That is, the monomer (I) and the polymer (I) may have an anionic group (A ０ ), it is also preferred that the alkyl group has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0141] Anionic group (A ０ ) is -SO ３ M ａ , -OSO ３ M ａ , -SO ２ M ａ , -COOM ａ , -SO ２ NR'CH ２ COOM ａ , -CH ２ OP (O) (OM ａ ) ２ , [-CH ２ O] ２ P(O)(OM ａ ), -CH ２ CH ２ OP (O) (OM ａ ) ２ , [-CH ２ CH ２ O] ２ P(O)(OM ａ ), -CH ２ CH ２ OSO ３ M ａ , -P(O)(OM ａ ) ２ , -SO ２ NR'CH ２ CH ２ OP (O) (OM ａ ) ２ , [-SO ２ NR'CH２ CH ２ O] ２ P(O)(OM ａ ), -CH ２ OSO ３ M ａ , -SO ２ NR'CH ２ CH ２ OSO ３ M ａ , or -C(CF ３ ) ２ O.M. ａ Among them, —SO ３ M ａ , -OSO ３ M ａ , -COOM ａ , -P(O)(OM ａ ) ２ or C(CF ３ ) ２ O.M. ａ is preferred, and -COOM ａ , -SO ３ M ａ , -OSO ３ M ａ or C(CF ３ ) ２ O.M. ａ is more preferred, and —SO ３ M ａ , -COOM ａ or P(O)(OM ａ ) ２ is more preferred, and —SO ３ M ａ or COOM ａ is particularly preferred, and -COOM ａ is most preferred.

[0142] M ａ represents H, a metal atom, NR ２ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ is H or an organic group.

[0143] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0144] M ａ is —H, a metal atom, or NR ２ ４ is preferred, and —H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR ２ ４ is more preferred, and —H, —Na, —K, —Li or NH ４ is more preferred, and —H, —Na, —K or NH ４ is even more preferred, and —H, —Na or NH ４ is particularly preferred, and —H or NH ４ is most preferred.

[0145] In the polymer (I), each polymer unit (I) may have a different anionic group or may have the same anionic group.

[0146] The monomer (I) is preferably a monomer represented by the general formula (Ia). The polymer (I) is preferably a polymer containing a polymerized unit (Ia) based on the monomer represented by the general formula (Ia). CF ２ ═CF—O—Rf ０ -A ０ (Ia) (wherein A ０ is an anionic group, and Rf ０ is a perfluorinated divalent linking group which may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and which optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0147] The monomer (I) is preferably a monomer represented by the general formula (Ib). The polymer (I) is preferably a polymer containing a polymerized unit (Ib) based on the monomer represented by the general formula (Ib). CH ２ =CH-O-Rf ０ -A ０ (Ib) (wherein, A ０ is an anionic group, and Rf ０ is a perfluorinated divalent linking group as defined in formula Ia.

[0148] In general formula (I), A ０is a sulfate group. ０ is, for example, —CH ２ OSO ３ M ａ , -CH ２ CH ２ OSO ３ M ａ , or -SO ２ NR'CH ２ CH ２ OSO ３ M ａ wherein R' is H or an alkyl group having 1 to 4 carbon atoms; M ａ is the same as above.

[0149] A ０ is a sulfate group, examples of the monomer represented by general formula (I) include CF ２ =CF(OCF ２ CF ２ CH ２ OSO ３ M ａ ), C.H. ２ =CH(O(CF ２ ) ４ CH ２ OSO ３ M ａ ), CF ２ =CF(O(CF ２ ) ４ CH ２ OSO ３ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) CH ２ OSO ３ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CH ２ OSO ３ M ａ ), C.H. ２ =CH(O(CF ２ ) ４ CH ２ OSO ３ M ａ ), CF２ =CF(OCF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OSO ３ M ａ ), C.H. ２ =CH(OCF ２ CF ２ CH ２ OSO ３ M ａ ), CF ２ =CF(OCF ２ CF ２ CF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OSO ３ M ａ ), C.H. ２ =CH(OCF ２ CF ２ CF ２ CH ２ OSO ３ M ａ In the above formula, M ａ is the same as above.

[0150] In general formula (I), A ０ In one preferred embodiment, A is a sulfonate group. ０ For example, -SO ３ M ａ wherein M ａ is the same as above.

[0151] A ０ is a sulfonate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ SO ３ M ａ ), CF ２ =CF(O(CF ２ ) ３ SO ３ M ａ ), CF ２ =CF(O(CF ２ )４ SO ３ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) SO ３ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ SO ３ M ａ ), C.H. ２ =CH(OCF ２ CF ２ SO ３ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ CF ２ SO ３ M ａ ), C.H. ２ =CH(O(CF ２ ) ４ SO ３ M ａ ), C.H. ２ =CH(O(CF ２ ) ３ SO ３ M ａ In the above formula, M ａ is the same as above.

[0152] In general formula (I), A ０ In one preferred embodiment, A is a sulfinate group. ０ For example, -SO ２ M ａ wherein M ａ is the same as above.

[0153] A ０ is a sulfinate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ SO ２ M ａ ), CF ２=CF(O(CF ２ ) ３ SO ２ M ａ ), CF ２ =CF(O(CF ２ ) ４ SO ２ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) SO ２ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ SO ２ M ａ ), C.H. ２ =CH(OCF ２ CF ２ SO ２ M ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ CF ２ SO ２ M ａ ), C.H. ２ =CH(O(CF ２ ) ４ SO ２ M ａ ), C.H. ２ =CH(O(CF ２ ) ３ SO ２ M ａ In the above formula, M ａ is the same as above.

[0154] In general formula (I), A ０ In one preferred embodiment, A is a carboxylate group. ０ For example, COOM ａ or SO ２ NR'CH ２ COOM ａ wherein R' is H or an alkyl group having 1 to 4 carbon atoms; M ａ is the same as above.０ is a carboxylate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ COOM ａ ), CF ２ =CF(O(CF ２ ) ３ COOM ａ ), CF ２ =CF(O(CF ２ ) ４ COOM ａ ), CF ２ =CF(O(CF ２ ) ５ COOM ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) COOM ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) O(CF ２ ) ｎ COOM ａ ) (n is greater than 1), CH ２ =CH(OCF ２ CF ２ COOM ａ ), C.H. ２ =CH(O(CF ２ ) ４ COOM ａ ), C.H. ２ =CH(O(CF ２ ) ３ COOM ａ ), CF ２ =CF(OCF ２ CF ２ SO ２ NR'CH ２ COOM ａ ), CF ２ =CF(O(CF ２ ) ４ SO ２ NR'CH ２ COOM ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) SO ２ NR'CH２ COOM ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ SO ２ NR'CH ２ COOM ａ ), C.H. ２ =CH(OCF ２ CF ２ SO ２ NR'CH ２ COOM ａ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ CF ２ SO ２ NR'CH ２ COOM ａ ), C.H. ２ =CH(O(CF ２ ) ４ SO ２ NR'CH ２ COOM ａ ), C.H. ２ =CH(O(CF ２ ) ３ SO ２ NR'CH ２ COOM ａ In the above formula, R' is H or an alkyl group having 1 to 4 carbon atoms, and M ａ is the same as above.

[0155] In general formula (I), A ０ In one preferred embodiment, A is a phosphate group. ０ Examples of the group include -CH ２ OP (O) (OM ａ ) ２ , [-CH ２ O] ２ P(O)(OM ａ ), -CH ２ CH ２ OP (O) (OM ａ ) ２ , [-CH ２ CH２ O] ２ P(O)(OM ａ ), [-SO ２ NR'CH ２ CH ２ O] ２ P(O)(OM ａ ) or SO ２ NR'CH ２ CH ２ OP (O) (OM ａ ) ２ wherein R' is an alkyl group having 1 to 4 carbon atoms, and M ａ is the same as above.

[0156] A ０ is a phosphate, the monomer represented by general formula (I) is CF ２ =CF(OCF ２ CF ２ CH ２ OP (O) (OM ａ ) ２ ), CF ２ =CF(O(CF ２ ) ４ CH ２ OP (O) (OM ａ ) ２ ), CF ２ =CF(OCF ２ CF (CF ３ ) CH ２ OP (O) (OM ａ ) ２ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CH ２ OP (O) (OM ａ ) ２ ), CF ２ =CF(OCF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OP (O) (OM ａ ) ２ ), CF ２ =CF(OCF ２ CF ２ CF２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OP (O) (OM ａ ) ２ ), C.H. ２ =CH(OCF ２ CF ２ CH ２ OP (O) (OM ａ ) ２ ), C.H. ２ =CH(O(CF ２ ) ４ CH ２ OP (O) (OM ａ ) ２ ), C.H. ２ =CH(O(CF ２ ) ３ CH ２ OP (O) (OM ａ ) ２ In the above formula, M ａ is the same as above.

[0157] In general formula (I), A ０ In one preferred embodiment, A is a phosphonate group. ０ is a phosphonate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ P(O)(OM ａ ) ２ ), CF ２ =CF(O(CF ２ ) ４ P(O)(OM ａ ) ２ ), CF ２ =CF(OCF ２ CF (CF ３ ) P (O) (OM ａ ) ２ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ P(O)(OM ａ ) ２ ), C.H. ２ =CH(OCF２ CF ２ P(O)(OM ａ ) ２ ), C.H. ２ =CH(O(CF ２ ) ４ P(O)(OM ａ ) ２ ), C.H. ２ =CH(O(CF ２ ) ３ P(O)(OM ａ ) ２ ) in which M ａ is the same as above.

[0158] The monomer (I) is preferably a monomer (1) represented by the general formula (1). The polymer (I) is preferably a polymer (1) containing a polymerized unit (1) based on the monomer represented by the general formula (1). CX ２ =CY(-CZ ２ -O-Rf-A) (1) (In the formula, X is the same or different and represents -H or F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z is the same or different and represents -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 2 to 100 carbon atoms and an ether bond. A is -COOM ａ , -SO ３ M ａ , -OSO ３ M ａ , -SO ２ M ａ , or C(CF ３ ) ２ O.M. ａ (M ａ is —H, a metal atom, —NR ２ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom.

[0159] 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 may be a copolymer with another monomer.

[0160] The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0161] In general formula (1), X is —H or F. Both Xs may be —F, or at least one X may be —H. For example, one X may be —F and the other may be —H, or both Xs may be —H.

[0162] In general formula (1), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The Y may be -H, -F or CF ３ is preferred, and —F is more preferred.

[0163] In general formula (1), Z's may be the same or different and are -H, -F, an alkyl group, or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The Z's may be -H, -F, or CF ３ is preferred, and —F is more preferred.

[0164] In the 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.

[0165] In the general formula (1), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond.

[0166] The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. The number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. The fluorine-containing alkylene group includes, for example, —CF ２ -, -CH ２ CF ２ -, -CF ２ CF ２ -, -CF ２ CH ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF ２ CH ２ -, -CF(CF ３ ) -, -CF(CF ３ )CF ２ -, -CF(CF ３ ) CH ２ The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0167] The number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorine-containing alkylene group having an ether bond is, for example, a group represented by the general formula: (In the formula, Z １ is F or CF ３ ;Z ２ and Z ３ are H or F; Z ４ is H, F or CF ３p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5).

[0168] Specific examples of the fluorine-containing alkylene group having an ether bond include —CF ２ CF (CF ３ ) OCF ２ CF ２ -, -CF(CF ３ )CF ２ -O-CF(CF ３ )-,-(CF(CF ３ )CF ２ -O) ｎ -CF (CF ３ )-(wherein n is an integer from 1 to 10), -CF(CF ３ )CF ２ -O-CF(CF ３ ) CH ２ -, -(CF(CF ３ )CF ２ -O) ｎ -CF (CF ３ ) CH ２ - (wherein n is an integer of 1 to 10), -CH ２ CF ２ CF ２ O-CH ２ CF ２ CH ２ -, -CF ２ CF ２ CF ２ O-CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ CH ２ -, -CF ２ CF ２ O-CF ２ -, -CF ２CF ２ O-CF ２ CH ２ The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0169] In the general formula (1), 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 represents H, a metal atom, NR ２ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ is H or an organic group).

[0170] R ２ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ More preferred are organic groups represented by the formula: １－４ More preferred are alkyl groups of the formula:

[0171] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred.

[0172] M ａ is H, a metal atom or NR ２ ４ is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR ２ ４ is more preferred, and H, Na, K, Li or NH ４ is more preferred, and H, Na, K or NH ４ is even more preferred, H, Na or NH ４ is particularly preferred, and H or NH ４ is most preferred.

[0173] A is -COOM ａ or SO ３M ａ is preferred, and -COOM ａ is more preferred.

[0174] Examples of the monomer represented by the general formula (1) include a monomer represented by the general formula (1a): ２ =CFCF ２ -O-(CF(CF ３ )CF ２ O) ｎ５ -CF (CF ３ )-A (1a) (wherein each X is the same and represents F or H, n5 represents 0 or an integer of 1 to 10, and A is as defined above).

[0175] In general formula (1a), n5 is preferably 0 or an integer from 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in that particles having a small primary particle size can be obtained.

[0176] In the production method of the present disclosure, the monomer represented by general formula (1a) may be copolymerized with another monomer, and the polymer (1) may be a homopolymer of the monomer represented by general formula (1a) or a copolymer with another monomer.

[0177] The monomer (1) is preferably a monomer represented by the general formula (1A). The polymerized unit (1) is preferably a polymerized unit (1A) based on a monomer represented by the general formula (1A). CH ２ =CF(-CF ２ —O—Rf-A) (1A) (wherein Rf and A are the same as defined above.)

[0178] In the production method of the present disclosure, the monomer represented by general formula (1A) may be copolymerized with another monomer, and the polymer (1) may be a homopolymer of the monomer represented by general formula (1A) or a copolymer with another monomer.

[0179] Specific examples of the monomer represented by formula (1A) include the monomer represented by the general formula: (In the formula, Z １ is F or CF ３ ;Z ２ and Z ３ are H or F; Z４ is H, F or CF ３ p1+q1+r1 is an integer of 0 to 10; s1 is 0 or 1; t1 is an integer of 0 to 5, provided that Z ３ and Z ４ are both H, then p1+q1+r1+s1 is not 0; A is the same as defined above). More specifically, etc. are preferred, among which It is preferable that:

[0180] The monomer represented by the general formula (1A) is a monomer represented by the general formula (1A) in which A is -COOM ａ It is preferable that ２ =CFCF ２ OCF (CF ３ ) COOM ａ , and C.H. ２ =CFCF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM ａ (In the formula, M ａ is as defined above.) ２ =CFCF ２ OCF (CF ３ ) COOM ａ is more preferred.

[0181] Further, examples of the monomer represented by general formula (1) include a monomer represented by the following formula: CF ２ =CFCF ２ -O-Rf-A (wherein Rf and A are the same as above)

[0182] More specifically, etc.

[0183] The monomer (I) is preferably a monomer (2) represented by the general formula (2). The polymer (I) is preferably a polymer (2) containing a polymer unit (2) based on the monomer represented by the general formula (2). CX ２=CY(-O-Rf-A) (2) (In the formula, X's are the same or different and each represents -H or F; Y represents -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf represents a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond or a keto group; and A is the same as defined above.)

[0184] In the production method of the present disclosure, the monomer (2) represented by general formula (2) may be copolymerized with another monomer. The polymer (2) may be a homopolymer of the monomer represented by general formula (2) or a copolymer with another monomer.

[0185] In general formula (2), X is —H or F. Both Xs may be —F, or at least one X may be —H. For example, one X may be —F and the other may be —H, or both Xs may be —H.

[0186] In general formula (2), Y is -H, -F, an alkyl group, or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. Y is -H, -F, or CF ３ is preferred, and —F is more preferred.

[0187] In general formula (2), it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be —H, and Y and Z may be —F.

[0188] In general formula (2), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, or a fluorine-containing alkylene group having a keto group having 2 to 100 carbon atoms. The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0189] The carbon number of the fluorine-containing alkylene group of Rf is preferably 2 or more, and more preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less. Examples of the fluorine-containing alkylene group include -CF ２ -, -CH ２ CF ２ -, -CF ２ CF ２ -, -CF ２ CH ２ -, -CF ２ CF ２ CH ２ -, -CF(CF ３ ) -, -CF(CF ３ )CF ２ -, -CF(CF ３ ) CH ２ -, -CF ２ CF ２ CF ２ -, CF ２ CF ２ CF ２ CF ２ The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0190] The number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less. The fluorine-containing alkylene group having an ether bond is, for example, a group represented by the general formula: (In the formula, Z １ is F or CF ３ ;Z ２ and Z ３ are H or F; Z ４ is H, F or CF ３ p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5).

[0191] Specific examples of the fluorine-containing alkylene group having an ether bond include —CF ２ CF (CF３ )OCF ２ CF ２ -、-CF ２ CF(CF ３ )OCF ２ CF ２ CF ２ -、-CF(CF ３ )CF ２ -O-CF(CF ３ )-、-(CF(CF ３ )CF ２ -O) ｎ -CF(CF ３ )-(where n is an integer from 1 to 10)、-CF(CF ３ )CF ２ -O-CF(CF ３ )CH ２ -、-(CF(CF ３ )CF ２ -O) ｎ -CF(CF ３ )CH ２ -(where n is an integer from 1 to 10)、-CH ２ CF ２ CF ２ O-CH ２ CF ２ CH ２ -、-CF ２ CF ２ CF ２ O-CF ２ -、-CF ２ CF ２ CF ２ O-CF ２ CF ２ -、-CF ２ CF ２ CF ２ O-CF ２ CF ２ CF ２ -、-CF ２ CF ２ CF ２ O-CF ２ CF ２ CH ２ -、-CF ２ CF ２ O-CF ２ -、-CF ２ CF ２ O-CF ２ CH ２The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0192] The number of carbon atoms in the fluorine-containing alkylene group having a keto group is preferably 3 or more. The number of carbon atoms in the fluorine-containing alkylene group having a keto group is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less.

[0193] Specific examples of the fluorine-containing alkylene group having a keto group include: ２ CF (CF ３ )CO-CF ２ -, -CF ２ CF (CF ３ )CO-CF ２ CF ２ -, -CF ２ CF (CF ３ )CO-CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３ )CO-CF ２ CF ２ CF ２ CF ２ The fluorine-containing alkylene group having a keto group is preferably a perfluoroalkylene group.

[0194] Water may be added to the keto group in the fluorine-containing alkylene group. Therefore, the monomer (2) may be a hydrate. Examples of the fluorine-containing alkylene group in which water is added to the keto group include —CF ２ CF (CF ３ )C(OH) ２ -CF ２ -, -CF ２ CF (CF ３ )C(OH) ２ -CF ２ CF ２ -, -CF ２ CF (CF ３ )C(OH) ２ -CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３)C(OH) ２ -CF ２ CF ２ CF ２ CF ２ --etc.

[0195] The monomer represented by general formula (2) is preferably at least one selected from the group consisting of monomers represented by general formulas (2a), (2b), (2c), (2d), (2e), (2f), and (2g). ２ =CF-O-(CF ２ ) ｎ１ -A (2a) (wherein n1 represents an integer of 1 to 10, and A is the same as defined above) CF ２ =CF-O-(CF ２ C (CF ３ ) F) ｎ２ -A (2b) (wherein n2 represents an integer of 1 to 5, and A is as defined above) CF ２ =CF-O-(CFX １ ) ｎ３ -A (2c) (wherein, X １ is F or CF ３ wherein n3 represents an integer of 1 to 10, and A is as defined above. ２ =CF-O-(CF ２ CFX １ O) ｎ４ -(CF ２ ) ｎ６ -A (2d) (wherein n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and A and X １ is the same as the definition above.) CF ２ =CF-O-(CF ２ CF ２ CFX １ O) ｎ５ -CF ２ CF ２ CF ２ -A (2e) (wherein n5 represents an integer of 0 to 10, and A and X １ is the same as the definition above.) CF ２ =CF-O-(CF ２ ) ｎ７ -O-(CF ２ ) ｎ８-A (2f) (wherein n7 represents an integer of 1 to 10, n8 represents an integer of 1 to 3, and A is as defined above.) CF ２ =CF[OCF ２ CF (CF ３ )] ｎ９ O (CF ２ ) ｎ１０ O[CF(CF ３ )CF ２ O] ｎ１１ CF (CF ３ )-A (2g) (wherein n9 represents an integer of 0 to 5, n10 represents an integer of 1 to 8, and n11 represents an integer of 0 to 5. A is as defined above.)

[0196] In the general formula (2a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.

[0197] Examples of the monomer represented by general formula (2a) include CF ２ =CF-O-CF ２ COOM ａ , C.F. ２ =CF(OCF ２ CF ２ COOM ａ ), CF ２ =CF(O(CF ２ ) ３ COOM ａ ), CF ２ =CF(OCF ２ CF ２ SO ３ M ａ ), CF ２ = CFOCF ２ SO ３ M ａ , C.F. ２ = CFOCF ２ CF ２ CF ２ SO ３ M ａ (In the formula, M ａ is the same as the definition above.

[0198] In general formula (2b), n2 is preferably an integer of 3 or less, from the viewpoint of the dispersion stability of the resulting composition.

[0199] In the general formula (2c), n3 is preferably an integer of 5 or less in terms of water solubility, and A is preferably -COOM ａ It is preferable that the above M ａ is H, Na or NH ４ It is preferable that:

[0200] In general formula (2d), X １ In terms of dispersion stability of the composition, -CF ３ n4 is preferably an integer of 5 or less in terms of water solubility, and A is preferably -COOM ａ Preferably, M ａ is H, Na or NH ４ It is preferable that:

[0201] Examples of the monomer represented by general formula (2d) include CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ COOM ａ , C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ COOM ａ , C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ COOM ａ , C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ SO ３ M ａ , C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ SO ３ M ａ , C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ SO３ M ａ (In the formula, M ａ , H, NH ４ or an alkali metal.

[0202] In the general formula (2e), n5 is preferably an integer of 5 or less from the viewpoint of water solubility, and A is preferably -COOM ａ Preferably, M ａ is H or NH ４ It is preferable that:

[0203] Examples of the monomer represented by general formula (2e) include CF ２ = CFOCF ２ CF ２ CF ２ COOM ａ (In the formula, M ａ is H, Na, NH ４ or an alkali metal.

[0204] In the general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, and A is preferably -COOM ａ or SO ３ M ａ It is preferable that -COOM ａ is more preferred. ａ is H, Na, K or NH ４ It is preferable that:

[0205] Examples of the monomer represented by general formula (2f) include CF ２ =CF-O-(CF ２ ) ３ -O-CF ２ -COOM ａ (In the formula, M ａ , H, NH ４ or an alkali metal.

[0206] In the general formula (2g), n9 is preferably an integer of 3 or less in terms of water solubility, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, and A is -COOM ａ or SO ３ M ａ It is preferable that -COOMａ is more preferred. ａ is H, Na, K or NH ４ It is preferable that:

[0207] Examples of the monomer represented by general formula (2g) include CF ２ = CFO (CF ２ ) ２ OCF (CF ３ ) COOM ａ , C.F. ２ = CFOCF ２ CF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM ａ , C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ OCF (CF ３ ) COOM ａ , C.F. ２ =CF[OCF ２ CF (CF ３ )] ２ O (CF ２ ) ２ O[CF(CF ３ )CF ２ O]CF(CF ３ ) COOM ａ , C.F. ２ =CF[OCF ２ CF (CF ３ )] ３ O (CF ２ ) ２ O[CF(CF ３ )CF ２ O] ３ CF (CF ３ ) COOM ａ (In the formula, M ａ , H, NH ４ or an alkali metal.

[0208] The monomer (I) is preferably a monomer (3) represented by the general formula (3). The polymer (I) is preferably a polymer (3) containing a polymer unit (3) based on the monomer represented by the general formula (3). CX ２=CY(-Rf-A) (3) (In the formula, X is the same or different and represents -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 2 to 100 carbon atoms and an ether bond; and A is the same as defined above.)

[0209] In the production method of the present disclosure, the monomer (3) represented by general formula (3) may be copolymerized with another monomer. The polymer (3) may be a homopolymer of the monomer represented by general formula (3) or a copolymer with another monomer.

[0210] The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0211] In general formula (3), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In general formula (3), at least one of X and Y preferably contains a fluorine atom.

[0212] The monomer represented by the general formula (3) is represented by the general formula (3a): CF ２ =CF-(CF ２ ) ｎ１ -A (3a) (wherein n1 represents an integer of 1 to 10, and A is as defined above), and a monomer represented by the general formula (3b): CF ２ =CF-(CF ２ C (CF ３ ) F) ｎ２ -A (3b) (wherein n2 represents an integer of 1 to 5, and A is as defined above) is preferred.

[0213] In the general formula (3a) and the general formula (3b), A is —SO ３ M ａ or COOM ａ is preferred, and M ａ represents H, a metal atom, NR ２ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. ２ represents H or an organic group.

[0214] In the general formula (3a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. ａ Preferably, M ａ is H or NH ４ It is preferable that:

[0215] Examples of the monomer represented by general formula (3a) include CF ２ =CFCF ２ COOM ａ (In the formula, M ａ is the same as the definition above.

[0216] In the general formula (3b), n2 is preferably an integer of 3 or less from the viewpoint of the dispersion stability of the resulting composition, and A is preferably -COOM ａ Preferably, M ａ is H or NH ４ It is preferable that:

[0217] Next, a preferred structure when m in general formula (I) is an integer of 2 or more will be described.

[0218] It is also preferred that the monomer (I) is at least one selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). It is also preferred that the polymer (I) is a polymer (4) containing polymerization units (4) based on at least one monomer selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). CF ２ =CF-CF ２ -O-Q Ｆ１ -CF(-Q Ｆ２ -CZ １ Z ２ -A) ２ (4a) (wherein, Z １ , Z ２ and A are the same as defined above, Q Ｆ１ and Q Ｆ２are 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. ２ =CF-O-Q Ｆ１ -CF(-Q Ｆ２ -CZ １ Z ２ -A) ２ (4b) (wherein, Z １ , Z ２ , A, Q Ｆ１ and Q Ｆ２ is the same as above)

[0219] The monomers represented by general formula (4a) and general formula (4b) include: etc.

[0220] The monomer (I) is preferably at least one selected from the group consisting of the monomer (1), the monomer (2), and the monomer (3), more preferably the monomer (1), and even more preferably the monomer (1A). 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 more preferably the polymer (1).

[0221] In the present disclosure, the monomer (I) may be copolymerized with another monomer. The polymer (I) may be a homopolymer consisting of only the polymerized unit (I), or may be a copolymer containing the polymerized unit (I) and a polymerized unit based on another monomer copolymerizable with the monomer represented by the general formula (I). From the viewpoint of solubility in an aqueous medium, a homopolymer consisting of only the polymerized unit (I) is preferred. The polymerized units (I) may be the same or different in each occurrence, and the polymer (I) may contain polymerized units (I) based on two or more different monomers represented by the general formula (I).

[0222] The other monomers include those represented by the general formula CFR=CR ２ (wherein R is independently H, F or a perfluoroalkyl group having 1 to 4 carbon atoms) is preferred. As the other monomer, a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms is preferred. As the other monomer, for example, CF ２ =CF ２, C.F. ２ = CFCl, CH ２ =CF ２ , CFH=CH ２ , CFH=CF ２ , C.F. ２ =CFCF ３ , C.H. ２ =CFCF ３ , C.H. ２ = CHCF ３ , CHF=CHCF ３ (E form), CHF=CHCF ３ Among them, tetrafluoroethylene (CF ２ =CF ２ ), chlorotrifluoroethylene (CF ２ =CFCl) and vinylidene fluoride (CH ２ =CF ２ ), and more preferably at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride. Therefore, the polymerized units based on the other monomer are preferably polymerized units based on tetrafluoroethylene. The polymerized units based on the other monomer may be the same or different in each occurrence, and polymer (I) may contain polymerized units based on two or more different other monomers.

[0223] The other monomers also include those represented by the general formula (n1-2): (In the formula, X １ , X ２ are the same or different and are H or F; X ３ are H, F, Cl, CH ３ or CF ３ ;X ４ , X ５ are the same or different and are H or F; a and c are the same or different and are 0 or 1. ３ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond).

[0224] Specifically, CH ２ =CFCF ２ -O-Rf ３ , C.F.２ ═CF—O—Rf ３ , C.F. ２ =CFCF ２ -O-Rf ３ , C.F. ２ =CF-Rf ３ , C.H. ２ =CH-Rf ３ , C.H. ２ =CH-O-Rf ３ (wherein, Rf ３ is the same as the above formula (n1-2).

[0225] Examples of the other monomer include a monomer of the formula (n2-1): (In the formula, X ９ is H, F or CH ３ ; Rf ４ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond). ４ The base is (wherein d3 is an integer of 1 to 4; e3 is an integer of 1 to 10), etc.

[0226] Examples of the other monomer include a monomer represented by formula (n2-2): CH ２ =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 2 to 100 carbon atoms and having an ether bond).

[0227] Specific examples of the monomer of general formula (n2-2) include: (wherein e6 is an integer of 1 to 10) are preferred.

[0228] More specifically, etc.

[0229] Others include those represented by the general formula (n2-3): CH ２ =CHCH ２ O-Rf ６ (n2-3) (wherein, Rf ６is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond), a fluorine-containing allyl ether represented by the general formula (n2-4): CH ２ =CH-Rf ７ (n2-4) (wherein, Rf ７ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond), and the like.

[0230] Specific examples of the monomers represented by general formulas (n2-3) and (n2-4) include: and the like monomers.

[0231] The polymer (I) usually has a terminal group. The terminal group is a terminal group generated during polymerization, and typical terminal groups are independently selected from hydrogen, iodine, bromine, linear or branched alkyl groups, and linear or branched fluoroalkyl groups, and may optionally contain at least one catenary heteroatom. The alkyl group or fluoroalkyl group preferably has 1 to 20 carbon atoms. These terminal groups are generally generated from the initiator or chain transfer agent used in forming the polymer (I), or are generated during the chain transfer reaction.

[0232] In the polymer (I), the content of the polymerized units (I) relative to all polymerized units is, in order of preference, 1.0 mol% or more, 3.0 mol% or more, 5.0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, and 90 mol% or more. The content of the polymerized units (I) is particularly preferably substantially 100 mol%, and the polymer (I) is most preferably composed only of the polymerized units (I).

[0233] In the polymer (I), the content of polymerization units based on other monomers copolymerizable with the monomer represented by general formula (I) is, in order of preference, 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, and 10 mol% or less, based on all polymerization units. It is particularly preferable that the content of polymerization units based on other monomers copolymerizable with the monomer represented by general formula (I) is substantially 0 mol%, and it is most preferable that the polymer (I) does not contain polymerization units based on other monomers.

[0234] The number average molecular weight of the polymer (I) is 0.1 × 10 ４ More than 0.2 × 10 ４ More preferably, 0.3 × 10 ４ More preferably, 0.4 × 10 ４ More preferably, 0.5 × 10 ４ More preferably, 1.0 x 10 ４ More preferably, 3.0 × 10 ４ More particularly, 3.1 × 10 ４ More than 75.0×10 is most preferable. ４ Preferably, 50.0 x 10 ４ More preferably, 40.0 x 10 ４ More preferably, 30.0 x 10 ４ The following is particularly preferred: 20.0 x 10 ４ The following are particularly preferred. The number average molecular weight and weight average molecular weight are values ​​calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. When measurement by GPC is not possible, the number average molecular weight of polymer (I) can be determined from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0235] The lower limit of the weight average molecular weight of the polymer (I) is, in order of preference, 0.2 × 10 ４ That's it, 0.4 x 10 ４That's it, 0.6 x 10 ４ That's it, 0.8 x 10 ４ That's it, 1.0 x 10 ４ That's it, 2.0 x 10 ４ That's it, 5.0 x 10 ４ That's it, 10.0 x 10 ４ That's it, 15.0 x 10 ４ That's it, 20.0 x 10 ４ That's it, 25.0 x 10 ４ The upper limit of the weight average molecular weight of the polymer (I) is, in order of preference, 150.0×10 ４ Below, 100.0 x 10 ４ Below, 60.0 x 10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ The following is the result.

[0236] The polymer (I) preferably has an ion exchange ratio (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the polymer main chain relative to the ionic group. ２ F) is not considered an ionizable group for purposes of determining IXR.

[0237] IXR is preferably 0.5 or more, more preferably 1 or more, even more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. IXR is more preferably 43 or less, even more preferably 33 or less, and particularly preferably 23 or less.

[0238] The ion exchange capacity of the polymer (I) is, in order of preference, 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.20 meq / g or more, more than 2.20 meq / g, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, and 3.50 meq / g or more. The ion exchange capacity is the content of ionic groups (anionic groups) in the polymer (I) and is calculated from the composition of the polymer (I).

[0239] In polymer (I), the ionic (anionic) groups are typically distributed along the polymer backbone. The polymer (I) comprises a polymer backbone with recurring side chains attached to the backbone, which preferably carry ionic groups.

[0240] Preferably, polymer (I) comprises ionic groups having a pKa of less than 10, more preferably less than 7. The ionic groups of polymer (I) are preferably selected from the group consisting of sulfonate, carboxylate, phosphonate, and phosphate.

[0241] The terms "sulfonate, carboxylate, phosphonate, and phosphate" are intended to refer to the respective salts or the respective acids capable of forming salts. When salts are used, preferably the salts are alkali metal salts or ammonium salts. A preferred ionic group is a sulfonate group.

[0242] The polymer (I) is preferably water-soluble. Water-soluble means the property of being easily dissolved or dispersed in an aqueous medium. The particle size of the water-soluble polymer (I) cannot be measured by, for example, dynamic light scattering (DLS), or the particle size is 5 nm or less.

[0243] The viscosity of an aqueous solution of polymer (I) is preferably 5.0 mPa.s or more, more preferably 8.0 mPa.s or more, even more preferably 10.0 mPa.s or more, particularly preferably 12.0 mPa.s or more, and most preferably 14.0 mPa.s or more, and is preferably 100.0 mPa.s or less, more preferably 50.0 mPa.s or less, even more preferably 25.0 mPa.s or less, and especially preferably 20.0 mPa.s or less.

[0244] The viscosity of the aqueous solution of polymer (I) can be determined by adjusting the content of polymer (I) in the aqueous solution to 33 mass % based on the aqueous solution, and measuring the viscosity of the obtained aqueous solution at 20°C using a tuning fork vibro viscometer (model number: SV-10) manufactured by A&D Co., Ltd.

[0245] The critical micelle concentration (CMC) of the polymer (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less.

[0246] The critical micelle concentration of the polymer (I) can be determined by measuring the surface tension, for example, using a surface tensiometer CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.

[0247] The acid value of the polymer (I) is preferably 60 or more, more preferably 90 or more, even more preferably 120 or more, particularly preferably 150 or more, and most preferably 180 or more. The upper limit is not particularly limited, but is preferably 300 or less.

[0248] The acid value of the polymer (I) is determined by the amount of anionic groups other than the acid functional groups of the polymer (I), such as -COOM ａ , -SO ３ M ａ , -OSO ３ M ａ or C(CF ３ ) ２ O.M. ａ (M ａ is a metal atom, NR ２ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ When the compound has a group (H or an organic group), these groups can be converted into acid groups and then measured by acid-base titration.

[0249] Compound (II) is represented by general formula (II): Ｘ -X Ａ -R ＦＡ１ -R ＦＡ２ -X Ａ -T Ｘ '(II) (wherein, R ＦＡ１ is -Rf １ ｐ -R Ｆ -O ｑ - and RＦＡ２ 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, and Rf １ and Rf ２ each independently represents a C optionally substituted by one or more fluorine atoms; １－６ each p is independently 0 or 1; each q is independently 0 or 1; X Ａ are each independently a single bond or a divalent to decavalent group, Ｘ and T Ｘ (i) each independently contains one or more of H, O, and Cl, and does not contain the anionic group; １ ~C ２４ (hydro)(fluoro)carbon groups, and (ii) at least one of the anionic groups described above. １ ~C ２４ (hydro)(fluoro)carbon groups.)

[0250] In formula (II), R ＦＡ１ is -Rf １ ｐ -R Ｆ -O ｑ - is.

[0251] In formula (II), R ＦＡ２ is -Rf ２ ｐ -R ＦＸ -O ｑ - is.

[0252] In formula (II), Rf １ and Rf ２ each independently represents a C optionally substituted by one or more fluorine atoms; １－６ It is an alkylene group.

[0253] The C optionally substituted with one or more fluorine atoms １－６ "C" in the alkylene group１－６ The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ alkylene groups, more preferably linear C １－３ It is an alkylene group.

[0254] Rf １ and Rf ２ is preferably a C substituted by one or more fluorine atoms １－６ is an alkylene group, more preferably C １－６ A perfluoroalkylene group, more preferably C １－３ It is a perfluoroalkylene group.

[0255] Above C １－６ The perfluoroalkylene group may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C １－３ A perfluoroalkylene group, more preferably a linear C １－３ Perfluoroalkylene groups, specifically —CF ２ -, -CF ２ CF ２ - or -CF ２ CF ２ CF ２ - is.

[0256] In the above formula, each p is independently 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0257] In the above formula, each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0258] In formula (II), R Ｆ is a divalent fluoropolyether group.

[0259] R Ｆ is preferably represented by the formula: -(OC ６ F １２ ) ａ - (OC ５ F １０ ) ｂ - (OC ４ F ８ ) ｃ - (OC３ R Ｆａ ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [In the formula: R Ｆａ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of occurrence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, all R Ｆａ is a hydrogen atom or a chlorine atom, then at least one of a, b, c, e and f is 1 or greater.]

[0260] R Ｆａ is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom. Ｆａ is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

[0261] a, b, c, d, e and f may each independently be an integer of preferably 0 to 100, more preferably an integer of 0 to 50.

[0262] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, even more preferably 20 or more, and may be, for example, 25 or more or 30 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0263] These repeating units may be linear or branched, and may contain a ring structure. For example, -(OC ６ F １２ )- is -(OCF ２ CF ２ CF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF３ ) CF ２ CF ２ CF ２ CF ２ ) -、 -(OCF ２ CF(CF ３ ) CF ２ CF ２ CF ２ ) -、 -(OCF ２ CF ２ CF(CF ３ ) CF ２ CF ２ ) -、 -(OCF ２ CF ２ CF ２ CF(CF ３ ) CF ２ ) -、 -(OCF ２ CF ２ CF ２ CF ２ CF(CF ３ )) - etc. may be. -(OC ５ F １０ ) - is, -(OCF ２ CF ２ CF ２ CF ２ CF ２ ) -、 -(OCF(CF ３ ) CF ２ CF ２ CF ２ ) -、 -(OCF ２ CF(CF ３ ) CF ２ CF ２ ) -、 -(OCF ２ CF ２ CF(CF ３ ) CF ２ ) -、 -(OCF ２ CF ２ CF ２ CF(CF ３ )) - etc. may be. -(OC ４ F ８ ) - is, -(OCF ２ CF ２ CF ２ CF ２ ) -、 -(OCF(CF ３ ) CF ２ CF ２ ) -、 -(OCF ２CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )) -, -(OC(CF ３ ) ２ CF ２ ) -, -(OCF ２ C (CF ３ ) ２ )-,-(OCF(CF ３ )CF(CF ３ ))-,-(OCF(C ２ F ５ )CF ２ )-and-(OCF ２ CF (C ２ F ５ ))-. ３ F ６ ) - (i.e., in the above formula, R Ｆａ is a fluorine atom) is -(OCF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ )-and-(OCF ２ CF (CF ３ ))-. ２ F ４ )- is -(OCF ２ CF ２ )-and-(OCF(CF ３ ))-.

[0264] The ring structure may be a three-, four-, five-, or six-membered ring as shown below. [In the formula, * indicates the bonding position.]

[0265] The ring structure may be preferably a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

[0266] The repeating unit having a ring structure may preferably be the following unit. [In the formula, * indicates the bonding position.]

[0267] In one embodiment, the repeating unit is linear.

[0268] In one embodiment, the repeat unit is branched.

[0269] In one embodiment, R Ｆ is a group represented by any one of the following formulas (f1) to (f6): ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ (f1) [wherein d is an integer of 1 to 200, and e is 0 or 1, preferably 0], -(OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f2) [wherein c and d each independently represent an integer of 0 or more and 30 or less, e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more, and the order of occurrence of each repeating unit enclosed in parentheses with c, d, e, or f is arbitrary in the formula.], - (R ６ -R ７ ) ｇ - (f3) [wherein, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, and g is an integer of 2 to 100. ], -(R ６ -R ７ ) ｇ -R ｒ - (R ７’ -R６’ ) ｇ’ - (f4) [wherein, R ６ is OCF ２ or O.C. ２ F ４ and R ７ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; ６’ is OCF ２ or O.C. ２ F ４ and R ７’ is O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R ｒ teeth, (wherein * indicates the bond position). ]; -(OC ６ F １２ ) ａ - (OC ５ F １０ ) ｂ - (OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ- (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] - (OC ６ F １２ ) ａ - (OC ５ F １０ ) ｂ - (OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e each independently are an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0270] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, and even more preferably 15 to 50, for example, an integer of 25 to 35. ３ F ６ is preferably (OCF ２ CF ２ CF ２ ), (OCF(CF ３ )CF ２ ) or (OCF ２ CF (CF ３ )), more preferably (OCF ２ CF ２ CF ２ In one embodiment, e is 0. In another embodiment, e is 1. (OC ２ F ４ ) is preferably (OCF ２ CF ２ ) or (OCF(CF ３ )), more preferably (OCF ２ CF ２)

[0271] In the formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the formula (f2) is preferably -(OCF ２ CF ２ CF ２ CF ２ ) ｃ -(OCF ２ CF ２ CF ２ ) ｄ -(OCF ２ CF ２ ) ｅ -(OCF ２ ) ｆ In another embodiment, formula (f2) is a group represented by -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ It may be a group represented by -.

[0272] In the above formula (f3), R ６ is preferably OC ２ F ４ In the above (f3), R ７ is preferably OC ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ or a combination of two or three groups independently selected from these groups, more preferably OC ３ F ６ or O.C. ４ F ８ OC ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ The combination of two or three groups independently selected from the group consisting of, but not limited to, —OC ２F ４ OC ３ F ６ -、-OC ２ F ４ OC ４ F ８ -、-OC ３ F ６ OC ２ F ４ -、-OC ３ F ６ OC ３ F ６ -、-OC ３ F ６ OC ４ F ８ -、-OC ４ F ８ OC ４ F ８ -、-OC ４ F ８ OC ３ F ６ -、-OC ４ F ８ OC ２ F ４ -、-OC ２ F ４ OC ２ F ４ OC ３ F ６ -、-OC ２ F ４ OC ２ F ４ OC ４ F ８ -、-OC ２ F ４ OC ３ F ６ OC ２ F ４ -、-OC ２ F ４ OC ３ F ６ OC ３ F ６ -、-OC ２ F ４ OC ４ F ８ OC ２ F ４ -、-OC ３ F ６ OC ２ F ４ OC ２ F４ -, -OC ３ F ６ O.C. ２ F ４ O.C. ３ F ６ -, -OC ３ F ６ O.C. ３ F ６ O.C. ２ F ４ -, and -OC ４ F ８ O.C. ２ F ４ O.C. ２ F ４ In the formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The g is preferably an integer of 50 or less. In the formula (f3), OC ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ may be either a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC ２ F ４ -OC ３ F ６ ) ｇ -or- (OC ２ F ４ -OC ４ F ８ ) ｇ - is.

[0273] In the above formula (f4), R ６ , R ７ and g have the same meanings as those in formula (f3) above, and have the same embodiments. ６’ , R ７’ and g′ are R ６ , R ７ and g have the same meaning and similar aspects. ｒ is preferably [wherein * indicates the bonding position], and more preferably [wherein * indicates the bonding position.]

[0274] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0275] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0276] In one embodiment, R Ｆ is a group represented by the above formula (f1).

[0277] In one embodiment, R Ｆ is a group represented by the above formula (f2).

[0278] In one embodiment, R Ｆ is a group represented by the above formula (f3) or (f4).

[0279] In one embodiment, R Ｆ is a group represented by the above formula (f3).

[0280] In one embodiment, R Ｆ is a group represented by the above formula (f4).

[0281] In one embodiment, R Ｆ is a group represented by the above formula (f5).

[0282] In one embodiment, R Ｆ is a group represented by the above formula (f6).

[0283] R ＦIn the formula, the ratio of e to f (hereinafter referred to as "e / f ratio") is preferably 0.1 to 10, more preferably 0.2 to 5, even more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85. By making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the more the stability of the compound can be improved.

[0284] In one embodiment, from the viewpoint of heat resistance, the e / f ratio may be preferably 1.0 or more, more preferably 1.0 to 2.0.

[0285] In formula (II), R ＦＸ is a divalent fluoropolyether group containing an anionic group. The anionic group includes anionic groups such as sulfate groups and carboxylate groups, as well as acid groups such as —COOH, —COONH ４ The anionic group includes a functional group that provides an anionic group such as an acid-base group, such as a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group, or a -C(CF ３ ) ２ O.M. ａ (In the formula, M ａ is —H, a metal atom, —NR ２ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ２ is H or an organic group.

[0286] R ＦＸ The fluoropolyether group in the formula (I) may be a group in which one or more hydrogen atoms of a polyether group have been substituted with fluorine atoms, and is preferably a perfluoropolyether group.

[0287] R ＦＸ As a repeating unit, (a1)-CF ２ CF (G ｘ )O- (b1)-CF(G ｘ )O- (c1)-CF ２ (CF ２ ) ｘ１ CF (Gｘ ) (CF ２ ) ｘ２ O- (X1 and X2 are zero or integers from 1 to 2, provided that X1+X2 is at least 1), where: G ｘ C contains at least one anionic group as detailed above １ ~C ５ and a divalent fluoropolyether group having a unit selected from the group consisting of: wherein the unit is a perfluoro(oxy)alkylene group.

[0288] In addition, R Ｆ and R ＦＸ The repeating units constituting the formula (I) may be present in any order.

[0289] In the above compound (II), R ＦＡ１ and R ＦＡ２ The number average molecular weight of the portion is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. ＦＡ１ and R ＦＡ２ The number average molecular weight of １９ The value is measured by F-NMR.

[0290] In formula (II), X Ａ represents the fluoropolyether moiety (R ＦＡ１ and R ＦＡ２ ) and a moiety containing an anionic group (T Ｘ and T Ｘ Therefore, the X Ａ may be a single bond or any other group as long as the compound represented by formula (II) can exist stably.

[0291] X Ａ are each independently a single bond or a divalent to decavalent group.

[0292] X Ａ are each independently preferably a single bond or a divalent to decavalent organic group.

[0293] In one embodiment, X Ａ does not contain a siloxane bond (—Si—O—Si—).

[0294] Above X Ａ The divalent to decavalent group in the formula (I) is preferably a divalent to octavalent group. In one embodiment, the divalent to decavalent group is preferably a divalent to tetravalent group, more preferably a divalent group. In another embodiment, the divalent to decavalent group is preferably a trivalent to octavalent group, more preferably a trivalent to hexavalent group.

[0295] In one embodiment, X Ａ is a single bond or a divalent group.

[0296] The divalent group is preferably an oxygen atom, a sulfur atom, NH, CO, or a divalent organic group, more preferably an oxygen atom or a divalent organic group, and even more preferably a divalent organic group.

[0297] In one embodiment, X Ａ is a trivalent to hexavalent group, preferably a trivalent to hexavalent organic group.

[0298] In one embodiment, X Ａ is a trivalent group, preferably a trivalent organic group.

[0299] In one embodiment, X Ａ is a single bond.

[0300] In another embodiment, X Ａ is a divalent organic group.

[0301] In one embodiment, X Ａ is, for example, a single bond or the following formula: -(R ５１ ) ｐ５ -(X ５１ ) ｑ５ - [In the formula: R ５１ is a single bond, -(CH ２ ) ｓ５ - or an o-, m- or p-phenylene group, preferably -(CH ２ ) ｓ５ -, s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; X ５１ is -(X ５２ ) ｌ５ represents -, and X ５２each independently represents an —O—, —S—, o-, m-, or p-phenylene group, —C(O)O—, —Si(R ５３ ) ２ -, -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ --, --CONR ５４ --, --O-CONR ５４ -, -NR ５４ - and - (CH ２ ) ｎ５ represents a group selected from the group consisting of -, ５３ are each independently a phenyl group, C １－６ Alkyl group or C １－６ represents an alkoxy group, preferably a phenyl group or C １－６ R is an alkyl group, more preferably a methyl group; ５４ are each independently a hydrogen atom, a phenyl group, or C １－６ represents an alkyl group (preferably a methyl group), m5 in each occurrence is independently an integer of 1 to 100, preferably an integer of 1 to 20, n5 in each occurrence is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the order of the repeating units enclosed in parentheses with p5 or q5 is arbitrary, and Ｘ and T Ｘ ' is bonded to. ]. Ａ (Typically X Ａ hydrogen atom) is a fluorine atom, C １－３ Alkyl group and C １－３ In a preferred embodiment, X Ａ is not substituted with these groups.

[0302] In a preferred embodiment, the X Ａare each independently -(R ５１ ) ｐ５ -(X ５１ ) ｑ５ -R ５２ - is. R ５２ is a single bond, -(CH ２ ) ｔ５ - or an o-, m- or p-phenylene group, preferably -(CH ２ ) ｔ５ t5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ５２ (Typically R ５２ hydrogen atom) is a fluorine atom, C １－３ Alkyl group and C １－３ In a preferred embodiment, R ５２ is not substituted with these groups.

[0303] Preferably, the above X Ａ are each independently a single bond, C １－２０ an alkylene group, —R ５１ -X ５３ -R ５２ - or -X ５４ -R ５ - [wherein, R ５１ and R ５２ has the same meaning as above, and X ５３ -O-, -S-, -C(O)O-, -CONR ５４ -, -O-CONR ５４ -, -Si(R ５３ ) ２ -, -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ -, -O-(CH ２ ) ｕ５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ -, -O-(CH ２ ) ｕ５ -Si(R ５３) ２ —O—Si(R ５３ ) ２ -CH ２ CH ２ -Si(R ５３ ) ２ —O—Si(R ５３ ) ２ -, -O-(CH ２ ) ｕ５ -Si(OCH ３ ) ２ OSi(OCH ３ ) ２ -, -CONR ５４ - (CH ２ ) ｕ５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ -, -CONR ５４ - (CH ２ ) 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 of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3; ５４ is -S-, -C(O)O-, -CONR ５４ -, -O-CONR ５４ -, -CONR ５４ - (CH ２ ) ｕ５ -(Si(R ５４ ) ２ O) ｍ５ -Si(R ５４ ) ２ -, -CONR ５４ - (CH ２ ) ｕ５ -N(R ５４ ) -, or -CONR ５４ -(o-, m- or p-phenylene)-Si(R ５４ ) ２- (wherein each symbol has the same meaning as above).

[0304] More preferably, the above X Ａ are each independently a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ５ -X ５３ -, -(CH ２ ) ｓ５ -X ５３ - (CH ２ ) ｔ５ - -X ５４ - or -X ５４ - (CH ２ ) ｔ５ - [wherein, X ５３ , X ５４ , s5 and t5 have the same meanings as above.]

[0305] More preferably, the above X Ａ are each independently a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ５ -X ５３ - (CH ２ ) ｔ５ - or -X ５４ - (CH ２ ) ｔ５ wherein each symbol has the same meaning as defined above.

[0306] In a preferred embodiment, the X Ａ are each independently a single bond C １－２０ an alkylene group, —(CH ２ ) ｓ５ -X ５３ - or -(CH ２ ) ｓ５ -X ５３ - (CH ２ ) ｔ５ - [wherein, X ５３ is -O-, -CONR ５４ -, or -O-CONR ５４ - and R ５４ are each independently a hydrogen atom, a phenyl group, or C １－６represents an alkyl group, s5 is an integer of 1 to 20, and t5 is an integer of 1 to 20.

[0307] In a preferred embodiment, the X Ａ are each independently -(CH ２ ) ｓ５ -O-(CH ２ ) ｔ５ --CONR ５４ - (CH ２ ) ｔ５ - [wherein, R ５４ are each independently a hydrogen atom, a phenyl group, or C １－６ represents an alkyl group, s5 is an integer of 1 to 20, and t5 is an integer of 1 to 20.

[0308] In one embodiment, the X Ａ are each independently a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ５ -O-(CH ２ ) ｔ５ -, -(CH ２ ) ｓ５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ - (CH ２ ) ｔ５ -, -(CH ２ ) ｓ５ -O-(CH ２ ) ｕ５ -(Si(R ５３ ) ２ O) ｍ５ -Si(R ５３ ) ２ - (CH ２ ) ｔ５ - or -(CH ２ ) ｓ５ -O-(CH ２ ) ｔ５ -Si(R ５３ ) ２ - (CH ２ ) ｕ５ -Si(R ５３ ) ２ -(C ｖ H２ｖ ) - [wherein, R ５３ , m5, s5, t5 and u5 are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 or 3.]

[0309] In the above formula, -(C ｖ H ２ｖ )- may be a straight chain or a branched chain, for example, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH(CH ３ ) -, -CH(CH ３ ) CH ２ -It can be.

[0310] Above X Ａ are each independently a fluorine atom, C １－３ Alkyl group and C １－３ Fluoroalkyl groups (preferably C １－３ In one embodiment, X may be substituted with one or more substituents selected from the group consisting of alkyl, aryl, aryls ... Ａ is non-substituted.

[0311] In one embodiment, X Ａ are each independently —O—C １－６ It may be other than an alkylene group.

[0312] In another embodiment, X Ａ Examples of the group include the following: [In the formula, R ４１ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C １－６ an alkoxy group, preferably a methyl group; D is —CH ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CF ２ O (CH ２ ) ３ -, -(CH ２ ) ２-, -(CH ２ ) ３ -, -(CH ２ ) ４ -, -CONH-(CH ２ ) ３ -, -CON(CH ３ )-(CH ２ ) ３ -, -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), and (In the formula, R ４２ are each independently a hydrogen atom, C １－６ or an alkyl group of C １－６ E represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group; ２ ) ｎ - (n is an integer of 2 to 6), and D is R of the molecular main chain. ＦＡ１ or R ＦＡ２ and E is bonded to R Ｓｉ binds to.]

[0313] Above X Ａ Specific examples of include: a single bond, —CH ２ OCH ２ -, -CH ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CH ２ O (CH ２ ) ４ -, -CH ２ O (CH ２ ) ５ -, -CH ２ O (CH ２ ) ６ -, -CH ２ O (CH ２ ) ３ Si(CH ３ ) ２ OSi(CH ３ ) ２ (CH ２ ) ２ -, -CH ２ O (CH２ ) ３ H ３ ) ２ HUNTER ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ３ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) １０ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２０ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ H ２ CHFOCF ２ -、 -CH ２ H２ CHFOCF ２ CF ２ -、 -CH ２ OCF ２ CHFOCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ -、 -CH ２ OCH ２CHFCF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCF ２ CHFOCF ２ CF ２ CF ２ -C(O)NH-CH ２ -、 -CH ２ OCH ２ (CH) ２ ) ７ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ３ -、 -CH ２ OCH ２ CH２ CH ２ H. ２ CH ３ ) ２ HUNTER ２ CH ３ ) ２ (CH ２ ) ３ -、 -CH ２ SO ２ CH ２ CH ２ H. ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CH ２ SO ２ CH ２ CH ２ H. ２ CH ３ ) ２ HUNTER ２ CH ３ ) ２ (CH ２ ) ２ -、 -(CH ２ ) ２ -Si(CH ３ ) ２ -(CH ２ ) ２ -、 -CH ２ -、 -(CH ２ ) ２ -、 -(CH ２ ) ３ -、 -(CH ２ ) ４ -、 -(CH ２ ) ５ -、 -(CH ２ ) ６ -、 -CO-、 -CONH-、 -CONH-CH ２ -、 -CONH-(CH ２ ) ２ -、 -CONH-(CH ２ ) ３ -、 -CONH-(CH ２ ) ４ -、 -CONH-(CH ２ ) ５ -、 -CONH-(CH２ ) ６ -, -CON(CH ３ )-CH ２ -, -CON(CH ３ )-(CH ２ ) ２ -, -CON(CH ３ )-(CH ２ ) ３ -, -CON(CH ３ )-(CH ２ ) ４ -, -CON(CH ３ )-(CH ２ ) ５ -, -CON(CH ３ )-(CH ２ ) ６ -, -CON(Ph)-CH ２ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ２ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ３ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ４ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ５ -(wherein Ph means phenyl), -CON(Ph)-(CH ２ ) ６ - (wherein Ph means phenyl), -CONH-(CH ２ ) ２ NH (CH ２ ) ３ -, -CONH-(CH ２ ) ６ NH (CH ２ ) ３ -, -CH ２ O-CONH-(CH ２ ) ３ -, -CH ２ O-CONH-(CH ２ ) ６ -, -S-(CH ２ ) ３ -, -(CH ２ ) ２H ２ ) ３ -、 -CONH-(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ３ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) １０ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２０Si(CH ３ )(CH ２ )(CH ２ )(CH ２ )-, -C(O)O-(CH ２ )(CH ３ )-, -C(O)O-(CH ２ )(CH ６ )-, -CH ２ -O-(CH ２ )(CH ３ )-Si(CH<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In yet another embodiment, X Ａ are each independently represented by the formula: -(R １６ ) ｘ１ -(CFR １７ ) ｙ１ - (CH ２ ) ｚ１ In the formula, x1, y1, and z1 each independently represent an integer of 0 to 10, the sum of x1, y1, and z1 is 1 or more, and the order of the repeating units enclosed in parentheses in the formula is arbitrary.

[0315] In the above formula, R １６ are each independently an oxygen atom, phenylene, carbazolylene, or —NR １８ - (wherein, R １８ represents a hydrogen atom or an organic group) or a divalent organic group. １８ is an oxygen atom or a divalent polar group.

[0316] The "divalent polar group" is not particularly limited, but examples thereof include -C(O)-, -C(=NR １９ )-, and -C(O)NR １９ - (wherein R １９ represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or n-propyl, which may be substituted with one or more fluorine atoms.

[0317] In the above formula, R １７ are each independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.

[0318] In addition, the above X Ａ The left side of each equation is R ＦＡ１ or R ＦＡ２ The right side is T Ｘ and T Ｘ '.

[0319] In yet another embodiment, X Ａ Examples of include the following groups: [In the formula, R ４１ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C １－６ The alkoxy group is preferably a methyl group, and each X Ａ In the group, any number of T's may be R ＦＡ１ or R ＦＡ２ The following groups are attached to: ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CF ２ O (CH ２ ) ３ -, -(CH ２ ) ２ -, -(CH ２ ) ３ -, -(CH ２ ) ４ -, -CONH-(CH ２ ) ３ -, -CON(CH ３ )-(CH ２ ) ３ -, -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), or [In the formula, R ４２ are each independently a hydrogen atom, C １－６ or an alkyl group of C １－６ represents an alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.], and some of the other Ts are R Ｓｉ and if present, the remaining Ts are each independently a methyl group, a phenyl group, C １－６ It is an alkoxy group, a radical scavenger group, or an ultraviolet absorbing group.]

[0320] The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, and triazines.

[0321] The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.

[0322] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include: Examples include:

[0323] In this embodiment, X Ａ may each independently be a trivalent to decavalent group.

[0324] In yet another embodiment, X Ａ Examples of include the following groups: [In the formula, R ２５ , R ２６ and R ２７ are each independently a divalent to hexavalent organic group, and R ２５ is at least one R ＦＡ１ or R ＦＡ２ and bonded to R ２６ and R ２７ Each of the groups is at least one R Ｓｉ binds to.]

[0325] In one embodiment, R ２５ is a single bond, C １－２０ Alkylene group, C ３－２０ Cycloalkylene group, C ５－２０ arylene group, —R ５７ -X ５８ -R ５９ -, -X ５８ -R ５９ - or -R ５７ -X５８ -. ５７ and R ５９ are each independently a single bond, C １－２０ Alkylene group, C ３－２０ a cycloalkylene group, or C ５－２０ The X is an arylene group. ５８ is —O—, —S—, —CO—, —O—CO— or —COO—.

[0326] In one embodiment, R ２６ and R ２７ are each independently a hydrocarbon or a group having at least one atom selected from N, O and S at the end or in the main chain of the hydrocarbon, and preferably C １－６ alkyl group, -R ３６ -R ３７ -R ３６ -, -R ３６ -CHR ３８ ２ -, etc. Here, R ３６ are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. ３７ is N, O or S, preferably N or O. ３８ 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. ４６ is N, O or S, preferably O.

[0327] In this embodiment, X Ａ may each independently be a trivalent to decavalent group.

[0328] In yet another embodiment, X Ａ is below: [In the formula, X ａ is a single bond or a divalent organic group.

[0329] Above X ａis a single bond or a divalent linking group directly bonded to the isocyanuric ring. ａ is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.

[0330] X ａ The following formula: -(CX １２１ X １２２ ) ｘ１ -(X ａ１ ) ｙ１ - (CX １２３ X １２４ ) ｚ１ - (wherein, X １２１ ~X １２４ are each independently H, F, OH, or —OSi(OR １２１ ) ３ (wherein three R １２１ are each independently an alkyl group having 1 to 4 carbon atoms, and ａ１ is —C(═O)NH—, —NHC(═O)—, —O—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, or —NHC(═O)NH— (the left side of each bond is CX １２１ X １２２ wherein x1 is an integer of 0 to 10, y1 is 0 or 1, and z1 is an integer of 1 to 10.

[0331] Above X ａ１ is preferably —O— or —C(═O)O—.

[0332] Above X ａ The following formula: -(CF ２ ) ｍ１１ - (CH ２ ) ｍ１２ -O-(CH ２ ) 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 -(CF ２ ) ｍ１４ - (CH ２ ) ｍ１５ -O-CH ２ CH(OH)-(CH ２ ) 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 -(CF ２ ) ｍ１７ - (CH ２ ) ｍ１８ - (wherein m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3), a group represented by -(CF ２ ) ｍ１９ - (CH ２ ) ｍ２０ -O-CH ２ CH(OSi(OCH ３ ) ３ )-(CH ２ ) 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), or -(CH ２ ) ｍ２２ A group represented by the formula: - (wherein m22 is an integer of 1 to 3) is particularly preferred.

[0333] Above X ａ is not particularly limited, but specifically includes -CH ２ -, -C ２ H ４ -, -C ３ H ６ -, -C ４ H ８ -, -C ４ H ８ -O-CH ２ -, -CO-O-CH ２ -CH(OH)-CH ２ -, - (CF ２ ) ｎ５ -(n5 is an integer from 0 to 4), -(CF ２ ) ｎ５ - (CH ２ ) ｍ５-(n5 and m5 each independently represents an integer of 0 to 4), -CF ２ CF ２ CH ２ OCH ２ CH(OH)CH ２ -, -CF ２ CF ２ CH ２ OCH ２ CH(OSi(OCH ３ ) ３ ) CH ２ - etc.

[0334] In this embodiment, X Ａ may each independently be a divalent or trivalent group.

[0335] In one embodiment, the compound (II) represented by formula (II) does not contain a siloxane bond (—Si—O—Si—).

[0336] The compound (II) is not particularly limited, but may be 5×10 ２ ~1 x 10 ５ From the viewpoint of polymerization stability, it is preferable that the lower limit of the number average molecular weight within this range is preferably 2,000 or more, more preferably 2,500 or more, and the upper limit is preferably 32,000 or less, more preferably 12,000 or less. The number average molecular weight of compound (II) is １９ The value is measured by F-NMR.

[0337] In one embodiment, the number average molecular weight of compound (II) may be preferably 500 or more, more preferably 1,000 or more, even more preferably 2,000 or more, still more preferably 3,000 or more, and may be preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, still more preferably 10,000 or less, particularly preferably 6,000 or less.

[0338] In another embodiment, the number average molecular weight of compound (II) may be preferably 4,000 or more, more preferably 5,000 or more, more preferably 6,000 or more, and may be preferably 30,000 or less, more preferably 10,000 or less.

[0339] Examples of compound (II) include compounds described in WO 2019 / 048394.

[0340] The content of the above-mentioned polymer compound in the TFE polymer composition of the present disclosure is preferably 100 mass ppm or less, more preferably 10 mass ppm or less, even more preferably 1 mass ppm or less, even more preferably 100 ppb or less, even more preferably 25 mass ppb or less, even more preferably 10 mass ppb or less, even more preferably 1 mass ppb or less, and particularly preferably less than the lower limit of quantification.Lower limit is not particularly limited, and can be the amount less than the lower limit of quantification.

[0341] The content of the polymer compound in the TFE-based polymer composition can be determined by solid-state NMR measurement. Methods for measuring the content of each polymer are described in JP-A-2012 / 082707, JP-A-2012 / 082703, JP-A-2012 / 082451, JP-A-2006 / 135825, JP-A-2004 / 067588, JP-A-2009 / 068528, JP-A-2004-075978, JP-A-2001-226436, JP-A-1992 / 017635, JP-A-2014 / 069165, JP-A-11-181009, etc. As a method for measuring the content of the above-mentioned polymer compound, the method for measuring the content of each polymer described therein can be used.

[0342] The TFE-based polymer composition of the present disclosure is preferably substantially free of water. This can suppress gas generation and deterioration of electrochemical device properties. Furthermore, a wide range of electrode active materials and solid electrolytes can be selected for combination, which is advantageous in terms of production processes. Being substantially free of water means that the water content of the TFE-based polymer composition is 0.010% by mass or less. The water content is preferably 0.005% by mass or less, more preferably 0.003% by mass or less, even more preferably 0.002% by mass or less, and even more preferably 0.001% by mass or less. The water content is measured by the following method. The mass of the TFE-based polymer composition is measured before and after heating at 150°C for 2 hours, and calculated according to the following formula. A sample is taken three times, and the values ​​are calculated for each sample, and the average is calculated and adopted. Water content (mass%)=[(mass (g) of TFE polymer composition before heating)−(mass (g) of TFE polymer composition after heating)] / (mass (g) of TFE polymer composition before heating)×100

[0343] The TFE-based polymer composition of the present disclosure preferably has fibrillation ability. Fibrillation ability refers to the property of easily fiberizing and forming fibrils by shear force. TFE-based polymer compositions with fibrillation ability can be paste-extruded, while TFE-based polymer compositions without fibrillation ability cannot. Therefore, whether a TFE-based polymer composition has fibrillation ability can be determined based on whether the composition is paste-extrudable. Specifically, this is determined by the following method. 60 g of the TFE-based polymer composition and 12.3 g of hydrocarbon oil (trade name: Isopar G (registered trademark), manufactured by ExxonMobil Corporation) as an extrusion aid are mixed in a polyethylene container for 3 minutes. The above mixture is filled into the cylinder of an extruder at room temperature (25±2°C), and a load of 0.47 MPa is applied to the piston inserted in the cylinder and maintained for 1 minute. Next, the mixture is extruded through an orifice at a ram speed of 20 mm / min. The ratio of the cross-sectional area of ​​the cylinder to the cross-sectional area of ​​the orifice is 100. If the beads break and cannot be extruded continuously, it is determined that there is no fibrillation ability (paste extrusion is not possible), and if the beads do not break and can be extruded continuously, it is determined that there is fibrillation ability (paste extrusion is possible).

[0344] The TFE-based polymer compositions of the present disclosure are preferably non-melt processable.

[0345] The TFE polymer composition of the present disclosure can form a composite sheet with more excellent strength, so that the endothermic peak temperature is preferably 333°C or higher, more preferably 335°C or higher, even more preferably 337°C or higher, even more preferably 340°C or higher, and preferably 350°C or lower, more preferably 346°C or lower.The endothermic peak temperature is the temperature corresponding to the minimum point in the heat of fusion curve obtained by carrying out differential scanning calorimetry (DSC) at a heating rate of 10°C / min for the TFE polymer composition that has no history of being heated to a temperature of 300°C or higher.When there are two or more minimum points in one melting peak, each of them is regarded as the endothermic peak temperature.

[0346] The TFE polymer composition of the present disclosure preferably has a melting point of 315° C. or higher, more preferably 320° C. or higher, even more preferably 323° C. or higher, even more preferably 325° C. or higher, and preferably 335° C. or lower, more preferably 330° C. or lower, in order to form a composite sheet having even greater strength. The melting point is the temperature corresponding to the minimum point in the heat of fusion curve obtained by carrying out differential scanning calorimetry (DSC) at a heating rate of 10° C. / min on a TFE polymer composition that has a history of being heated to a temperature of 300° C. or higher.

[0347] The TFE polymer composition of the present disclosure can form a composite sheet having better strength, so that its standard specific gravity (SSG) is preferably 2.280 or less, more preferably 2.250 or less, even more preferably 2.220 or less, even more preferably 2.200 or less, even more preferably 2.190 or less, especially preferably 2.180 or less, and particularly preferably 2.170 or less.The SSG is also preferably 2.130 or more.The SSG is measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895 89.

[0348] In order to further improve the electrical properties of the TFE polymer composition of the present disclosure, the 1.0% mass loss temperature is preferably 492°C or higher, more preferably 493°C or higher, even more preferably 494°C or higher, even more preferably 495°C or higher, and may be 550°C or lower. The 1.0% mass loss temperature is a value measured by the following method. About 10 mg of a TFE polymer composition that has not been heated to a temperature of 300°C or higher is precisely weighed, placed in a dedicated aluminum pan, and measured using a TG / DTA (differential thermal / thermogravimetric simultaneous analyzer). The 1.0% mass loss temperature is the temperature corresponding to the point at which a weight loss of 1.0% by mass occurs when the aluminum pan is heated in an air atmosphere in a temperature range from 25°C to 600°C at a rate of 10°C / min.

[0349] In order to further improve the electrical properties of the TFE polymer composition of the present disclosure, the 0.1% mass loss temperature is preferably 400°C or higher, more preferably 401°C or higher, even more preferably 402°C or higher, even more preferably 403°C or higher, and may be 450°C or lower. The 0.1% mass loss temperature is a value measured by the following method. About 10 mg of a TFE polymer composition that has not been heated to a temperature of 300°C or higher is precisely weighed, placed in a dedicated aluminum pan, and measured using a TG / DTA (differential thermal / thermogravimetric simultaneous analyzer). The 1.0% mass loss temperature is determined as the temperature at which a 0.1% mass loss occurs when the aluminum pan is heated in an air atmosphere in a temperature range from 25°C to 600°C at a rate of 10°C / min.

[0350] The TFE-based polymer composition of the present disclosure may have a heat stability index (TII) of 10 or more. A TFE-based polymer composition having a TII of 10 or more can be obtained by using a hydrocarbon surfactant. The TII is preferably 15 or more, more preferably 20 or more, even more preferably 25 or more, even more preferably 30 or more, even more preferably 35 or more, and particularly preferably 40 or more. The TII is also preferably 50 or less. The TII is measured in accordance with ASTM D 4895-89.

[0351] The TFE polymer composition of the present disclosure may have an average secondary particle diameter of 350 μ m or more, preferably 400 μ m or more, more preferably 450 μ m or more, and also preferably 1000 μ m or less, more preferably 900 μ m or less, even more preferably 800 μ m or less, even more preferably 700 μ m or less, particularly preferably 600 μ m or less.The average secondary particle diameter is measured according to JIS K 6891.

[0352] The TFE polymer composition of the present disclosure preferably has an apparent density of 0.40 g / ml or more, more preferably 0.43 g / ml or more, from the viewpoint of excellent handleability, and the upper limit is not particularly limited, but may be 0.70 g / ml. The apparent density is measured in accordance with JIS K 6892.

[0353] The form of the TFE polymer composition of the present disclosure is not limited, but is preferably powder, because it can be mixed with electrode active material or solid electrolyte without using a large amount of dispersion medium.It should be noted that the TFE polymer composition can also be in the form other than powder, for example, can be dispersion liquid.

[0354] The TFE polymer composition of the present disclosure can be suitably produced by subjecting a TFE polymer to a fluorination treatment.

[0355] Above-mentioned treated TFE polymer can be suitably produced by the production method comprising the following steps: prepare the aqueous dispersion of TFE polymer by emulsion polymerization; coagulate above-mentioned aqueous dispersion to obtain wet powder; and dry above-mentioned wet powder.

[0356] The step (A) is preferably, for example, a step (A1) in which TFE is emulsion-polymerized in an aqueous medium in the presence of an anionic fluorine-containing surfactant to obtain an aqueous dispersion of a TFE-based polymer.

[0357] The emulsion polymerization in step (A1) can be carried out by known method.For example, in the presence of anionic fluorine-containing surfactant and polymerization initiator, the emulsion polymerization of the monomers required for constituting the above-mentioned TFE polymer is carried out in aqueous medium, thereby obtaining the aqueous dispersion that contains the particles (primary particles) of the above-mentioned TFE polymer.In the above-mentioned emulsion polymerization, if necessary, chain transfer agent, buffering agent, pH adjuster, stabilizing aid, dispersion stabilizer, radical scavenger etc. can be used.

[0358] The emulsion polymerization can be carried out, for example, in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator. The emulsion polymerization can be carried out by charging an aqueous medium, the anionic fluorine-containing surfactant, monomers, and other additives as necessary into a polymerization reactor, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of polymerization initiator to initiate the polymerization reaction. After the start of the polymerization reaction, additional monomers, polymerization initiators, chain transfer agents, the surfactants, etc. may be added depending on the purpose.

[0359] The polymerization initiator is not particularly limited as long as it can generate radicals in the polymerization temperature range, and can use known oil-soluble and / or water-soluble polymerization initiator.Furthermore, it can also be combined with reducing agent etc. to initiate polymerization as redox.The concentration of the polymerization initiator is suitably determined according to the type of monomer, the molecular weight of the target TFE polymer and reaction rate.

[0360] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0361] The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, and the like. Also usable are di(ω-hydro-dodecafluoroheptanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di(ω-chloro Representative examples include di[perfluoro(or fluorochloro)acyl]peroxides such as di(ω-hexafluorobutyryl)peroxide, di(ω-chlorodecafluorohexanoyl)peroxide, di(ω-chlorotetradecafluorooctanoyl)peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl)peroxide, di(trichlorooctafluorohexanoyl)peroxide, di(tetrachloroundecafluorooctanoyl)peroxide, di(pentachlorotetradecafluorodecanoyl)peroxide, and di(undecachlorodotriacontafluorodocosanoyl)peroxide.

[0362] The water-soluble radical polymerization initiator may be a known water-soluble peroxide, such as ammonium salts, potassium salts, or sodium salts of persulfuric acid, perborate, perchloric acid, perphosphoric acid, or percarbonate, t-butyl permaleate, t-butyl hydroperoxide, or disuccinic acid peroxide. Among these, ammonium persulfate and disuccinic acid peroxide are preferred. A reducing agent such as sulfites or sulfites may also be contained, and the amount used may be 0.1 to 20 times the amount of the peroxide.

[0363] The amount of the water-soluble radical polymerization initiator to be added is not particularly limited, but may be added all at once, stepwise, or continuously at the beginning of the polymerization in an amount (for example, several ppm relative to the water concentration) that does not significantly reduce the polymerization rate. The upper limit is a range in which the reaction temperature can be increased while removing heat from the equipment using the heat of polymerization reaction, and a more preferred upper limit is a range in which the heat of polymerization reaction can be removed from the equipment. In terms of easily obtaining the above-mentioned properties, the amount of polymerization initiator to be added is preferably an amount equivalent to 0.1 ppm or more of the aqueous medium, more preferably an amount equivalent to 1.0 ppm or more, and also preferably an amount equivalent to 100 ppm or less, more preferably an amount equivalent to 10 ppm or less.

[0364] For example, when polymerization is carried out at a low temperature of 30°C or less, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator. Examples of oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, and bromates. Examples of reducing agents include sulfites, bisulfites, bromates, diimines, and oxalic acid. Examples of persulfates include ammonium persulfate and potassium persulfate. Examples of sulfites include sodium sulfite and ammonium sulfite. 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 redox initiator combination. Examples of copper salts include copper(II) sulfate, and examples of iron salts include iron(II) sulfate.

[0365] The redox initiator preferably has an oxidizing agent that is permanganic acid or a salt thereof, a persulfate, manganese triacetate, a cerium (IV) salt, or a bromic acid or a salt thereof, and a reducing agent that is a dicarboxylic acid or a salt thereof, or a diimine. More preferably, the oxidizing agent is permanganic acid or a salt thereof, a persulfate, or a bromic acid or a salt thereof, and the reducing agent is a dicarboxylic acid or a salt thereof.

[0366] Examples of the redox initiator include combinations such as potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, manganese triacetate / oxalic acid, manganese triacetate / ammonium oxalate, cerium ammonium nitrate / oxalic acid, and cerium ammonium nitrate / ammonium oxalate. When using a redox initiator, either an oxidizing agent or a reducing agent may be charged into a polymerization vessel in advance, and then the other may be added continuously or intermittently to initiate polymerization. For example, when potassium permanganate / oxalic acid is used, it is preferable to charge oxalic acid into a polymerization vessel and then continuously add potassium permanganate thereto. Note that, when referring to redox initiators in this specification, "potassium permanganate / oxalic acid" refers to a combination of potassium permanganate and oxalic acid. The same applies to other compounds.

[0367] The redox initiator is 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 persulfates, permanganates, cerium (IV) salts, and bromates, more preferably permanganates, and particularly preferably potassium permanganate. The reducing agent that is a salt is more preferably at least one selected from the group consisting of oxalates, malonates, succinates, glutarates, and bromates, more preferably oxalates, and particularly preferably ammonium oxalate.

[0368] Specifically, the redox initiator is preferably at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, manganese triacetate / ammonium oxalate, and cerium ammonium nitrate / ammonium oxalate, more preferably at least one selected from the group consisting of potassium permanganate / oxalic acid, potassium permanganate / ammonium oxalate, potassium bromate / ammonium sulfite, and cerium ammonium nitrate / ammonium oxalate, and even more preferably potassium permanganate / oxalic acid.

[0369] When a redox initiator is used, the oxidizing agent and the reducing agent may be added all at once at the beginning of the polymerization, or the reducing agent may be added all at once at the beginning of the polymerization and the oxidizing agent may be added continuously, or the oxidizing agent may be added all at once at the beginning of the polymerization and the reducing agent may be added continuously, or both the oxidizing agent and the reducing agent may be added continuously.

[0370] When one of the above redox polymerization initiators is added at the beginning of polymerization and the other is added continuously, the rate of addition is preferably gradually reduced in order to obtain a TFE-based polymer having a low SSG, and further, the addition is preferably stopped during the polymerization, and the timing for stopping the addition is preferably before 20 to 40% by mass of the total TFE consumed in the polymerization reaction is consumed.

[0371] When a redox initiator is used as a polymerization initiator, the amount of oxidizing agent added to the aqueous medium is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, even more preferably 0.5 ppm or more, even more preferably 1 ppm or more, particularly preferably 5 ppm or more, particularly preferably 10 ppm or more, and preferably 10,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 100 ppm or less, and even more preferably 50 ppm or less. The amount of reducing agent added is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, even more preferably 3 ppm or more, even more preferably 5 ppm or more, particularly preferably 10 ppm or more, and preferably 10,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 100 ppm or less, and even more preferably 50 ppm or less. When a redox initiator is used in the emulsion polymerization, the polymerization temperature is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower. The polymerization temperature is preferably 10° C. or higher, more preferably 20° C. or higher, and even more preferably 30° C. or higher.

[0372] As the polymerization initiator, a water-soluble radical polymerization initiator and a redox initiator are preferred, since the above-mentioned properties can be easily obtained.

[0373] The aqueous medium is a reaction medium for polymerization and refers to a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as an alcohol, an ether, or a ketone, and / or a fluorine-containing organic solvent having a boiling point of 40° C. or lower.

[0374] In the emulsion polymerization, a nucleating agent, a chain transfer agent, a buffer, a pH adjuster, a stabilizing aid, a dispersion stabilizer, a radical scavenger, a decomposing agent for the polymerization initiator, a dicarboxylic acid, etc. may be used, if necessary.

[0375] The emulsion polymerization is preferably carried out with the addition of a nucleating agent for the purpose of adjusting the particle size. The nucleating agent is preferably added before the start of the polymerization reaction. As the nucleating agent, a known agent can be used, and for example, at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents is preferred, and a nonionic surfactant is more preferred.

[0376] The fluoropolyether may be, for example, a perfluoropolyether (PFPE) acid or a salt thereof. The perfluoropolyether (PFPE) acid or a salt thereof may have any chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Two or more types of fluorocarbon groups may be present in the molecule. A representative structure has a repeating unit represented by the following formula: (-CFCF ３ -CF ２ -O-) ｎ (-CF ２ -CF ２ -CF ２ -O-) ｎ (-CF ２ -CF ２ -O-) ｎ -(-CF ２ -O-) ｍ (-CF ２ -CFCF ３ -O-) ｎ -(-CF ２ -O-) ｍ

[0377] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed therein, the PFPE acid or its salt may have a carboxylic acid group or a salt thereof at one or both ends. The PFPE acid or its salt may also have a sulfonic acid or phosphonic acid group or a salt thereof at one or both ends. The PFPE acid or its salt may also have a different group at each end. For monofunctional PFPEs, the other end of the molecule is usually perfluorinated but may contain a hydrogen or chlorine atom. The PFPE acid or its salt has at least two ether oxygens, preferably at least four ether oxygens, and even more preferably at least six ether oxygens. Preferably, at least one of the fluorocarbon groups separating the ether oxygens, more preferably at least two of such fluorocarbon groups, has two or three carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. Also preferably, the PFPE acid or salt thereof has a total of at least 15 carbon atoms, for example, the preferred minimum value of n or n+m in the repeating unit structure is at least 5. Two or more of the PFPE acids or salts thereof having acid groups at one or both termini may be used in the manufacturing method of the present disclosure. The PFPE acid or salt thereof preferably has a number average molecular weight of less than 6,000 g / mol.

[0378] In view of being able to further increase the molecular weight of TFE polymer and improve the strength of composite sheet, it is preferable to add radical scavenger or decomposition agent of polymerization initiator to carry out the emulsion polymerization.After the start of polymerization reaction, preferably, the decomposition agent of radical scavenger or polymerization initiator is added before 10% by mass or more, preferably 20% by mass or more of the total TFE consumed in polymerization reaction is polymerized, and also preferably before 50% by mass or less, preferably 40% by mass or less is polymerized.When carrying out depressurization and repressurization as described later, it is preferable to add it afterwards.

[0379] The radical scavenger is a compound that does not have the ability to reinitiation after addition or chain transfer to the free radicals in the polymerization system. Specifically, a compound that easily undergoes chain transfer reaction with a primary radical or a propagating radical to generate a stable radical that does not subsequently react with the monomer, or a compound that easily undergoes an addition reaction with a primary radical or a propagating radical to generate a stable radical, is used. The activity of what is generally called a chain transfer agent is characterized by the chain transfer constant and the reinitiation efficiency, and among chain transfer agents, those with a reinitiation efficiency of almost 0% are called radical scavengers. The radical scavenger can also be described as, for example, a compound whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant and whose reinitiation efficiency is essentially 0%. "Reinitiation efficiency is essentially 0%" means that the generated radical turns the radical scavenger into a stable radical. Preferably, the compound has a chain transfer constant (Cs) (= chain transfer rate constant (kc) / polymerization rate constant (kp)) with TFE at polymerization temperature of more than 0.1, and the chain transfer constant (Cs) of the compound is more preferably 0.5 or more, even more preferably 1.0 or more, even more preferably 5.0 or more, and particularly preferably 10 or more.

[0380] Examples of the radical scavenger include aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl ２) is preferred. Examples of aromatic hydroxy compounds include unsubstituted phenol, polyhydric phenol, salicylic acid, m- or p-salicylic acid, gallic acid, naphthol, etc. Examples of the unsubstituted phenol include o-, m-, or p-nitrophenol, o-, m-, or p-aminophenol, p-nitrosophenol, etc. Examples of polyhydric phenols include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, naphthresorcinol, etc. Examples of aromatic amines include o-, m-, or p-phenylenediamine, benzidine, etc. Examples of the quinone compounds include o-, m-, or p-benzoquinone, 1,4-naphthoquinone, alizarin, etc. Examples of thiocyanates include ammonium thiocyanate (NH ４ Examples of the radical scavenger include potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN), etc. Among these, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

[0381] The amount of the radical scavenger added is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration, from the viewpoint of appropriately reducing the standard specific gravity. A more preferred lower limit is 10% (molar basis), and even more preferred is 15% (molar basis). A more preferred upper limit is 400% (molar basis), and even more preferred is 300% (molar basis).

[0382] The polymerization initiator decomposer may be any compound capable of decomposing the polymerization initiator 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 preferred. Examples of sulfites include sodium sulfite and ammonium sulfite. Examples of copper salts include copper(II) sulfate, and examples of iron salts include iron(II) sulfate. The amount of decomposer added is preferably an amount equivalent to 3 to 500% (molar basis) of the initiator concentration, from the viewpoint of appropriately reducing the standard specific gravity. A more preferred lower limit is 10% (molar basis), and even more preferred is 15% (molar basis). A more preferred upper limit is 400% (molar basis), and even more preferred is 300% (molar basis).

[0383] The emulsion polymerization may be carried out in the presence of 5 to 500 ppm of dicarboxylic acid relative to the aqueous medium, preferably 10 to 200 ppm, in order to reduce the amount of coagulation produced during polymerization. If the amount of dicarboxylic acid relative to the aqueous medium is too small, sufficient effects may not be obtained, while if the amount is too large, chain transfer reactions may occur, resulting in a low molecular weight polymer. The amount of dicarboxylic acid is more preferably 150 ppm or less. The dicarboxylic acid may be added before the start of the polymerization reaction or during the polymerization.

[0384] As the dicarboxylic acid, for example, one represented by the general formula: HOOCRCOOH (wherein R represents an alkylene group having 1 to 5 carbon atoms) is preferred, and succinic acid, malonic acid, glutaric acid, adipic acid, and pimelic acid are more preferred, with succinic acid being even more preferred.

[0385] In the emulsion polymerization, the polymerization temperature and polymerization pressure are appropriately determined depending on the type of monomer used, the molecular weight of the target TFE polymer, and 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.Moreover, it is more preferably 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.More preferably, it is 5.0 MPaG or lower, and even more preferably 3.0 MPaG or lower.

[0386] When VDF is used as the modified monomer, in the emulsion polymerization, the VDF concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, since the above-mentioned physical properties can be easily obtained. The concentration may also be 15 mol% or less, preferably 6.0 mol% or less, more preferably 5.0 mol% or less, even more preferably 3.0 mol% or less, and particularly preferably 1.0 mol% or less. The VDF concentration may then be maintained until the end of the polymerization reaction, or pressure relief may be performed during the reaction. VDF is preferably charged all at once before the start of polymerization, but a portion may be added continuously or intermittently after the start of polymerization.

[0387] When VDF is used as the modified monomer, it is preferable not to release the pressure in the emulsion polymerization after VDF is charged into the polymerization vessel until the polymerization is completed, thereby allowing VDF to remain in the system until the end of the polymerization, and further increasing the strength of the resulting composite sheet using the TFE-based polymer.

[0388] When HFP is used as a modified monomer, in the emulsion polymerization, 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%, since the above-mentioned physical properties can be easily obtained. Furthermore, the HFP concentration in the gas in the reactor at the time when 40% by mass of the total TFE consumed in the polymerization reaction is polymerized 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 portion may be charged before the start of polymerization and added continuously or intermittently after the start of polymerization. By allowing HFP to remain until the end of the polymerization reaction, the extrusion pressure is reduced, even though the strength of the resulting mixture sheet using the TFE-based polymer is high.

[0389] When HFP is used as a modified monomer, in the emulsion polymerization, in order to further improve the strength of the composite sheet using the obtained TFE-based polymer, it is preferable to depressurize before 5 to 40 mass% of the total TFE consumed in the polymerization reaction is polymerized, and then repressurize only with TFE.The depressurization is preferably carried out so that the pressure in the reactor is 0.2 MPaG or less, more preferably 0.1 MPaG or less, and even more preferably 0.05 MPaG or less.It is also preferable to carry out so that the pressure is 0.0 MPaG or more.In addition, the depressurization and repressurization may be carried out multiple times.Depressurization may be carried out using a vacuum pump until reduced pressure is reached.

[0390] When CTFE is used as modified monomer, in the above-mentioned emulsion polymerization, the CTFE concentration in the gas in reactor at the start of polymerization (when adding initiator) is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, because it can easily obtain each of the above-mentioned properties.Above-mentioned concentration is also preferably 3.0 mol% or less, more preferably 1.0 mol% or less.Above-mentioned CTFE concentration can be maintained until the end of polymerization reaction, or can be depressurized during the process.It is preferable to charge CTFE all at once before the start of polymerization, but can also be added partly continuously or intermittently after the start of polymerization.

[0391] When CTFE is used as the modified monomer, in the emulsion polymerization, after CTFE is introduced into the polymerization vessel, it is preferable not to carry out depressurization until the polymerization is completed.Therefore, CTFE can be left in the system until the end of the polymerization, and the strength of the composite sheet using the obtained TFE-based polymer can be further increased.

[0392] Step (A) is also preferably step (A2) of emulsion-polymerizing TFE in an aqueous medium in the presence of a hydrocarbon surfactant to obtain an aqueous dispersion of a TFE-based polymer.

[0393] In the hydrocarbon surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0394] Step (A2) preferably comprises a step of carrying out emulsion polymerization of tetrafluoroethylene alone, or emulsion polymerization of tetrafluoroethylene and a modifying monomer copolymerizable with tetrafluoroethylene, in an aqueous medium in the presence of a specific hydrocarbon surfactant, and a step of continuously adding the specific hydrocarbon surfactant in the above step.

[0395] The continuous addition of a specific hydrocarbon surfactant means, for example, adding the specific hydrocarbon surfactant over time, without interruption, or in portions, rather than all at once. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxy groups), or a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxy groups) that has been subjected to radical treatment or oxidation treatment. The radical treatment may be any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxy groups). For example, the radical treatment may be a treatment in which deionized water and a hydrocarbon surfactant are added to a reactor, the reactor is sealed, the system is purged with nitrogen, the reactor is heated and pressurized, a polymerization initiator is added, the mixture is stirred for a certain period of time, and the reactor is depressurized to atmospheric pressure and then cooled. Above-mentioned oxidation treatment is the treatment that oxidizing agent is added to hydrocarbon surfactant that has one or more carbonyl groups (but excluding the carbonyl group in carboxyl group).As oxidizing agent, for example, oxygen, ozone, hydrogen peroxide water, manganese oxide (IV), potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide etc. can be enumerated.By above-mentioned production method, even if no conventional fluorine-containing surfactant is used, it is possible to produce TFE polymer that has the same molecular weight as that of the production method that uses conventional fluorine-containing surfactant.

[0396] In the above-mentioned production method, the step of continuously adding the specific hydrocarbon surfactant is preferably that when the solid content of the TFE polymer formed in aqueous medium is less than 0.60 mass%, the hydrocarbon surfactant is started to be added into aqueous medium.When the solid content is 0.5 mass% or less, the specific hydrocarbon surfactant is preferably started to be added into aqueous medium.When the solid content is 0.3 mass% or less, the specific hydrocarbon surfactant is more preferably started to be added when the solid content is 0.2 mass% or less, even more preferably started to be added when the solid content is 0.1 mass% or less, and particularly preferably started to be added at the start of polymerization.The solid content is the concentration relative to the total of aqueous medium and TFE polymer.

[0397] In the step of continuously adding the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant added is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium, more preferably 0.05% by mass at the lower limit, even more preferably 0.1% by mass at the lower limit, more preferably 5% by mass at the upper limit, and even more preferably 1% by mass at the upper limit.

[0398] In the process of emulsion polymerization of tetrafluoroethylene alone or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with tetrafluoroethylene in an aqueous medium in the presence of the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant is preferably large, and is preferably 0.0001 to 10 mass% relative to 100 mass% of the aqueous medium.A more preferred lower limit is 0.001 mass%, and a more preferred upper limit is 1 mass%.If it is less than 0.0001 mass%, the dispersing force may be insufficient, and if it exceeds 10 mass%, the 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 depending on the type of monomer used, the molecular weight of the target TFE polymer, etc.

[0399] The specific hydrocarbon surfactants include those represented by the formula: R-X (wherein R is a fluorine-free organic group having 1 to 2000 carbon atoms and one or more carbonyl groups (excluding carbonyl groups in carboxy groups), and X is -OSO ３ X １ , -COOX １ or -SO ３ X １ (X １ represents 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 (preferably an organic group not containing fluorine), and may be the same or different. )) is preferred. R preferably has 500 or less carbon atoms, more preferably 100 or less, even more preferably 50 or less, and even more preferably 30 or less. The specific hydrocarbon surfactant is a surfactant represented by the following formula (a): (In the formula, 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, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond (preferably an organic group not containing fluorine), and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. ２ａ and R ３ａ are independently a single bond or a divalent linking group. １ａ , R ２ａ and R ３ａ has a total of 6 or more carbon atoms. ａ represents H, a metal atom, NR ４ａ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ａ are H or organic groups (preferably fluorine-free organic groups), and may be the same or different. １ａ , R ２ａ and R３ａ any two of which may be bonded to each other to form a ring; a surfactant (a) represented by the following formula (b): (In the formula, R １ｂ R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. ２ｂ and R ４ｂ are independently H or a substituent. ３ｂ is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. X ｂ represents H, a metal atom, NR ５ｂ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ５ｂ are H or organic groups (preferably fluorine-free organic groups), and may be the same or different. １ｂ , R ２ｂ , R ３ｂ and R ４ｂ Any two of the groups may be bonded to each other to form a ring. L represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｂ -B-*, -NR ６ｂ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｂ -B-, -NR ６ (excluding the carbonyl group contained in CO—B—), B is a single bond or an alkylene group 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. * represents -OSO ３ X ｂ (b) a surfactant represented by the following formula (c): (In the formula, R １ｃis a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond (preferably an organic group not containing fluorine), and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. ２ｃ and R ３ｃ are independently a single bond or a divalent linking group. １ｃ , R ２ｃ and R ３ｃ has a total of 5 or more carbon atoms. ｃ Ha, -COOX ｃ or -SO ３ X ｃ (X ｃ represents H, a metal atom, NR ４ｃ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ｃ R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. １ｃ , R ２ｃ and R ３ｃ any two of which may be bonded to each other to form a ring; a surfactant (c) represented by the following formula (d): (In the formula, R １ｄ R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. ２ｄ and R ４ｄ are independently H or a substituent. ３ｄ is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. A ｄ is -SO ３ X ｄ or -COOX ｄ (X ｄ represents H, a metal atom, NR ５ｄ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ５ｄ R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. １ｄ , R ２ｄ , R ３ｄ and R ４ｄ Any two of the groups may be bonded to each other to form a ring. L represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), B is a single bond or an alkylene group 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. ｄ and a surfactant (d) represented by the following formula (e): (In the formula, R １ｅ ~R ５ｅ represents H or a monovalent substituent, provided that R １ｅ and R ３ｅ At least one of the groups represented by the general formula: -Y ｅ -R ６ｅ a group represented by R ２ｅ and R ５ｅ At least one of the groups represented by the general formula: -X ｅ -A ｅ or a group represented by the general formula: -Y ｅ -R ６ｅ In addition, X represents a group represented by the formula: ｅ A is the same or different in each occurrence and is a divalent linking group or bond; ｅ is the same or different in each occurrence and represents -COOM ｅ , -SO ３ M ｅ or -OSO ３ M ｅ (Mｅ represents H, a metal atom, NR ７ｅ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ｅ is H or an organic group (preferably an organic group not containing fluorine); Y ｅ is the same or different in each occurrence and represents -S(=O) ２ -, -O-, -COO-, -OCO-, -CONR ８ｅ - and -NR ８ｅ a divalent linking group selected from the group consisting of CO—, or a bond, R ８ｅ is H or an organic group (preferably a fluorine-free organic group); R ６ｅ R may be the same or different in each occurrence and represents an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms; １ｅ ~R ５ｅ Any two of the groups may be bonded to each other to form a ring.

[0400] The surfactant (a) will now be described.

[0401] In formula (a), R １ａ is a linear or branched alkyl group having one or more carbon atoms, or a cyclic alkyl group having three or more carbon atoms. When the alkyl group has three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. That is, CH ３ The alkyl group also includes acyl groups such as an acetyl group represented by -C(=O)-. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. R １ａIn the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to —C(═O)—, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0402] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocyclic ring. ３ —C(═O)—CH ２ The group represented by - has 3 carbon atoms, and ３ -C(=O)-C ２ H ４ -C(=O)-C ２ H ４ The group represented by - has 7 carbon atoms, and CH ３ The group represented by —C(═O)— has 2 carbon atoms.

[0403] In the alkyl group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferable that the alkyl group is not substituted with any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０１ａ (In the formula, R １０１ａ The alkyl group may be one in which 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms are substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0404] In the formula, R ２ａ and R ３ａ are independently a single bond or a divalent linking group. ２ａ and R ３ａ are preferably each independently a single bond, a linear or branched alkylene group having one or more carbon atoms, or a cyclic alkylene group having three or more carbon atoms. ２ａ and R ３ａThe alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0405] In the alkylene group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group containing no fluorine), but it is preferable that the alkylene group is not substituted with any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０２ａ (In the formula, R １０２ａ The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0406] R １ａ , R ２ａ and R ３ａ R has a total number of carbon atoms of 6 or more. The total number of carbon atoms is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. １ａ , R ２ａ and R ３ａ Any two of these may be bonded to each other to form a ring.

[0407] In formula (a), X ａ represents H, a metal atom, NR ４ａ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ａ is H or an organic group (preferably an organic group not containing fluorine). ４ａ may be the same or different. ４ａ The organic group in R is preferably an alkyl group. ４ａis preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. X ａ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ４ａ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ａ NH ４ In this case, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0408] Examples of the surfactant (a) include the following surfactants: ａ is as described above.

[0409]

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417] The surfactant (a) can be produced, for example, by the production method described in WO 2020 / 022355.

[0418] Next, the surfactant (b) will be described.

[0419] In formula (b), R １ｂ R is a linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, and an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. １ｂ In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to —C(═O)—, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0420] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0421] R １ｂ The substituent that the alkyl group as the group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0422] R １ｂ The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0423] R １ｂAs the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not have a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent is even more preferred, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) is most preferred.

[0424] In formula (b), R ２ｂ and R ４ｂ are independently H or a substituent. ２ｂ and R ４ｂ may be the same or different.

[0425] R ２ｂ and R ４ｂ The substituent as is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0426] R ２ｂ and R ４ｂ The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0427] R ２ｂ and R ４ｂThe alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and a methyl group (—CH ３ ) or an ethyl group (—C ２ H ５ ) is particularly preferred.

[0428] R ２ｂ and R ４ｂ are each independently preferably H or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not containing a substituent, and are each independently preferably H, a methyl group (—CH ３ ) or an ethyl group (—C ２ H ５ ) is even more preferred, with H being especially preferred.

[0429] In formula (b), R ３ｂ is an alkylene group having 1 to 10 carbon atoms which may have a substituent. ３ｂ When there are a plurality of, they may be the same or different.

[0430] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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.

[0431] 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 more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and a methylene group (—CH ２ -), ethylene group (-C ２ H ４ -), isopropylene group (-CH(CH ３ ) CH ２ -) or propylene group (-C ３ H ６ -) is more preferred.

[0432] R １ｂ , R ２ｂ , R ３ｂ and R ４ｂ Any two of may be bonded to each other to form a ring, but it is preferable that they do not form a ring.

[0433] In formula (b), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, still more preferably an integer of 5 to 25, and particularly preferably an integer of 5 to 9 or 11 to 25.

[0434] In formula (b), p and q are independently an integer of 0 or greater. 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.

[0435] The sum of n, p, and q is preferably an integer of 5 or greater. The sum of n, p, and q is more preferably an integer of 8 or greater. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and even more preferably an integer of 40 or less.

[0436] In formula (b), X ｂ represents H, a metal atom, NR ５ｂ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ５ｂ is H or an organic group (preferably an organic group not containing fluorine). ５ｂ may be the same or different. ５ｂ The organic group in R is preferably an alkyl group. ５ｂ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. X ｂ is a metal atom or NR ５ｂ ４ (R ５ｂ X may be as defined above. ｂ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ５ｂ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ｂ NH ４ In this case, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0437] In formula (b), L represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｂ -B-*, -NR ６ｂ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｂ -B-, -NR ６ｂ (excluding the carbonyl group contained in CO—B—), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R ６ｂis H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group preferably has 1 to 5 carbon atoms. ６ｂ is preferably H or a methyl group. * represents —OSO ３ X ｂ This refers to the side that binds to the

[0438] L is preferably a single bond.

[0439] The surfactant (b) may be a compound represented by the following formula: (In the formula, R １ｂ , R ２ｂ , L, n and X ｂ is as described above.) is preferred.

[0440] The surfactant (b) may be, for example, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ C(O)CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ OSO ３ Na, CH ３ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ I'm sorry ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ P.S. ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ H、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Li, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ K、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO３ NH ４ 、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH(CH ３ ) ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ I'm sorry ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ P.S. ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ H、 CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ OSO ３ Li, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ K、 CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ NH ４ 、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ OSO ３ Na and the like.

[0441] The surfactant (b) can be produced, for example, by the production method described in WO 2020 / 022355.

[0442] Next, the surfactant (c) will be described.

[0443] In formula (c), R １ｃ is a linear or branched alkyl group having one or more carbon atoms, or a cyclic alkyl group having three or more carbon atoms. When the alkyl group has three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. That is, CH ３ The alkyl group also includes acyl groups such as an acetyl group represented by -C(=O)-. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. R １ｃ In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to —C(═O)—, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0444] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocyclic ring. ３ —C(═O)—CH ２ The group represented by - has 3 carbon atoms, and ３ -C(=O)-C ２ H ４ -C(=O)-C ２ H ４ The group represented by - has 7 carbon atoms, and CH ３ The group represented by —C(═O)— has 2 carbon atoms.

[0445] In the alkyl group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferable that the alkyl group is not substituted with any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０１ｃ (In the formula, R １０１ｃ The alkyl group may be one in which 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms are substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0446] In formula (c), R ２ｃ and R ３ｃ are independently a single bond or a divalent linking group. ２ｃ and R ３ｃ are preferably each independently a single bond, a linear or branched alkylene group having one or more carbon atoms, or a cyclic alkylene group having three or more carbon atoms. ２ｃ and R ３ｃ The alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0447] In the alkylene group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond (preferably an organic group containing no fluorine), but it is preferable that the alkylene group is not substituted with 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 １０２ｃThe alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0448] R １ｃ , R ２ｃ and R ３ｃ R has a total carbon number of 5 or more. The total carbon number is preferably 7 or more, more preferably 9 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. １ｃ , R ２ｃ and R ３ｃ Any two of these may be bonded to each other to form a ring.

[0449] In formula (c), in the formula, A ｃ Ha, -COOX ｃ or -SO ３ X ｃ (X ｃ represents H, a metal atom, NR ４ｃ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ｃ R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. ４ｃ The organic group in R is preferably an alkyl group. ４ｃ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. X ｃ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ４ｃ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ｃ NH ４ In this case, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0450] Examples of the surfactant (c) include the following surfactants: ｃ is as described above.

[0451]

[0452]

[0453]

[0454]

[0455]

[0456]

[0457]

[0458]

[0459] The surfactant (c) can be produced, for example, by the production method described in WO 2020 / 022355.

[0460] Next, the surfactant (d) will be described.

[0461] In formula (d), R １ｄ R is a linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, and an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. １ｄIn the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to —C(═O)—, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0462] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0463] R １ｄ The substituent that the alkyl group as the group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0464] R １ｄ The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0465] R １ｄ As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not have a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent is even more preferred, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) is most preferred.

[0466] In formula (d), R ２ｄ and R ４ｄare independently H or a substituent. ２ｄ and R ４ｄ may be the same or different.

[0467] R ２ｄ and R ４ｄ The substituent as is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0468] R ２ｄ and R ４ｄ The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0469] R ２ｄ and R ４ｄ The alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and a methyl group (—CH ３ ) or an ethyl group (—C ２ H ５ ) is particularly preferred.

[0470] R ２ｄ and R ４ｄ are each independently preferably H or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not containing a substituent, and are each independently preferably H, a methyl group (—CH ３ ) or an ethyl group (—C ２ H ５) is even more preferred, with H being especially preferred.

[0471] In formula (d), R ３ｄ is an alkylene group having 1 to 10 carbon atoms which may have a substituent. ３ｄ When there are a plurality of, they may be the same or different.

[0472] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0473] 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 more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and a methylene group (—CH ２ -), ethylene group (-C ２ H ４ -), isopropylene group (-CH(CH ３ ) CH ２ -) or propylene group (-C ３ H ６ -) is more preferred.

[0474] R １ｄ , R ２ｄ , R ３ｄ and R ４ｄ Any two of these may be bonded to each other to form a ring.

[0475] In formula (d), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and even more preferably an integer of 5 to 25.

[0476] In formula (d), p and q are independently an integer of 0 or greater. 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.

[0477] The sum of n, p, and q is preferably an integer of 6 or greater. The sum of n, p, and q is more preferably an integer of 8 or greater. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and even more preferably an integer of 40 or less.

[0478] In formula (d), A ｄ is -SO ３ X ｄ or -COOX ｄ (X ｄ represents H, a metal atom, NR ５ｄ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ５ｄ R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. ５ｄ The organic group in R is preferably an alkyl group. ５ｄ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are preferred. X ｄ is a metal atom or NR ５ｄ ４ (R ５ｄ X may be as defined above. ｄ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ５ｄ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４is most preferred. ｄ NH ４ In this case, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the TFE-based polymer or the final product.

[0479] In formula (d), L represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R ６ｄ is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group more preferably has 1 to 5 carbon atoms. ６ｄ is more preferably H or a methyl group. ｄ This refers to the side that binds to the

[0480] L is preferably a single bond.

[0481] Examples of the surfactant (d) include CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３C(O)CH ２ CH ２ CH ２ CH ２ CH ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ CH ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２CH ２ CH ２ CH ２ CH ２ CH ２ COONa, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ Yes, yes ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ Yes, yes ３ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ Yes, yes ３ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ Yes, yes ３ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ Yes, yes ３ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ Yes, yes ３ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ Yes, yes ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ２ CH ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ I'm sorry ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ Yes, yes ３ C(O)CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ P.S. ２ Yes, yes ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COOH、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COOLi、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ P. ４ 、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２C(CH ３ ) ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, (CH ３ ) ３ CC(O)CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ I'm sorry ２ SO ３ Na, CH ３ C(O)CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ P.S. ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ H、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ K、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ SO ３ Li, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ NH ４ , C.H. ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(CH ３ ) ２ SO ３ Na and the like.

[0482] The surfactant (d) can be produced, for example, by the production method described in WO 2020 / 022355.

[0483] Next, the surfactant (e) will be described.

[0484] In formula (e), R １ｅ ~R ５ｅ represents H or a monovalent substituent, provided that R １ｅ and R ３ｅ At least one of the groups represented by the general formula: -Y ｅ -R ６ｅ a group represented by R ２ｅ and R ５ｅ At least one of the groups represented by the general formula: -X ｅ -A ｅ or a group represented by the general formula: -Y ｅ -R ６ｅ R represents a group represented by the formula: １ｅ ~R ５ｅ Any two of these may be bonded to each other to form a ring.

[0485] R １ｅThe substituent that the alkyl group as the group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0486] R １ｅ The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0487] R １ｅ As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not have a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent is even more preferred, and a methyl group (—CH ３ ) or an ethyl group (—C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) is most preferred.

[0488] The monovalent substituent includes a group represented by the general formula: -Y ｅ -R ６ｅ a group represented by the general formula: -X ｅ -A ｅ a group represented by the formula: -H, optionally substituted C １－２０ an alkyl group of —NH ２ , -NHR ９ｅ (R ９ｅ is an organic group (preferably an organic group not containing fluorine), —OH, —COOR ９ｅ (R ９ｅis an organic group (preferably an organic group not containing fluorine) or —OR ９ｅ (R ９ｅ is preferably an organic group (preferably an organic group not containing fluorine). The alkyl group preferably has 1 to 10 carbon atoms.

[0489] R ９ｅ As for C １－１０ or an alkyl group of C １－１０ The alkylcarbonyl group represented by the formula C is preferred. １－４ or an alkyl group of C １－４ An alkylcarbonyl group of the formula is more preferred.

[0490] In the formula, X ｅ R may be the same or different in each occurrence and represents a divalent linking group or a bond. ６ｅ does not contain any of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X ｅ is preferably a divalent linking group containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0491] X ｅ Examples include -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—, C １－１０ An alkylene group or a bond represented by the formula R ８ｅ represents H or an organic group (preferably an organic group not containing fluorine).

[0492] R ８ｅ The organic group in R is preferably an alkyl group. ８ｅ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ More preferred are organic groups represented by the formula: １－４ More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0493] In formula (e), A ｅis the same or different in each occurrence and represents -COOM ｅ , -SO ３ M ｅ or -OSO ３ M ｅ (M ｅ represents H, a metal atom, NR ７ｅ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ｅ is H or an organic group (preferably an organic group not containing fluorine). ７ｅ may be the same or different. ｅ Ha-COOM ｅ This is one of the preferred embodiments.

[0494] R ７ｅ The organic group in R is preferably an alkyl group. ７ｅ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ More preferred are organic groups represented by the formula: １－４ More preferred are alkyl groups of the following formula: Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0495] M ｅ is H, a metal atom or NR ７ｅ ４ is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR ７ｅ ４ is more preferred, and H, Na, K, Li or NH ４ is more preferred, Na, K or NH ４ is even more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred.

[0496] In formula (e), Y ｅ is the same or different in each occurrence and represents -S(=O) ２ -, -O-, -COO-, -OCO-, -CONR ８ｅ - and -NR ８ｅa divalent linking group selected from the group consisting of CO—, or a bond, R ８ｅ represents H or an organic group (preferably an organic group not containing fluorine).

[0497] Y ｅ Examples of the alkyl group include a bond, —O—, —COO—, —OCO—, and —CONR. ８ｅ - and -NR ８ｅ A divalent linking group selected from the group consisting of -CO- is preferred, and a divalent linking group selected from the group consisting of a bond, -COO-, and -OCO- is more preferred.

[0498] R ８ｅ The organic group in R is preferably an alkyl group. ８ｅ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ More preferred are organic groups represented by the formula: １－４ More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0499] In formula (e), R ６ｅ In each occurrence, R may be the same or different and represent an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms. ６ｅ The organic group (preferably an organic group containing no fluorine) preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

[0500] R ６ｅ The alkyl group of R may contain one or more groups selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms, but does not contain these groups at the terminal of the alkyl group. ６ｅ The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0501] R ６ｅ As the general formula: -R １０ｅ-CO-R １１ｅ a group represented by the general formula: -R １０ｅ -COO-R １１ｅ a group represented by the general formula: -R １１ｅ a group represented by the general formula: -R １０ｅ -NR ８ｅ CO-R １１ｅ or a group represented by the general formula: -R １０ｅ -CONR ８ｅ -R １１ｅ (wherein R ８ｅ represents H or an organic group (preferably an organic group not containing fluorine). １０ｅ is an alkylene group, R １１ｅ is preferably an alkyl group which may have a substituent. ６ｅ As the general formula: -R １０ｅ -CO-R １１ｅ A group represented by the following formula is more preferred.

[0502] R ８ｅ The organic group in R is preferably an alkyl group. ８ｅ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ More preferred are organic groups represented by the formula: １－４ More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0503] R １０ｅ The number of carbon atoms in the alkylene group of R is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. １０ｅ The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0504] R １１ｅ The number of carbon atoms in the alkyl group of may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, even more preferably 1 to 10, still more preferably 1 to 8, particularly preferably 1 to 6, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. １１ｅThe alkyl group of R is preferably composed of only primary, secondary and tertiary carbon atoms, and particularly preferably composed of only primary and secondary carbon atoms. １１ｅ As the alkyl group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, and a methyl group is most preferred.

[0505] In formula (e), R ２ｅ and R ５ｅ At least one of the groups represented by the general formula: -X ｅ -A ｅ and the A is a group represented by ｅ Ha-COOM ｅ In one preferred embodiment,

[0506] As the surfactant (e), a compound represented by general formula (e-1), a compound represented by general formula (e-2), or a compound represented by general formula (e-3) is preferred, and a compound represented by general formula (e-1) or a compound represented by general formula (e-2) is more preferred.

[0507] General formula (e-1): (In the formula, R ３ｅ ~R ６ｅ , X ｅ , A ｅ and Y ｅ (As mentioned above.)

[0508] General formula (e-2): (In the formula, R ４ｅ ~R ６ｅ , X ｅ , A ｅ and Y ｅ (As mentioned above.)

[0509] General formula (e-3): (In the formula, R ２ｅ , R ４ｅ ~R ６ｅ , X ｅ , A ｅ and Y ｅ (As mentioned above.)

[0510] General formula: -X ｅ -A ｅ Examples of the group represented by the formula: ｅ , -R １２ｅ COOMｅ 、 -SO ３ M ｅ 、 -OSO ３ M ｅ 、 -R １２ｅ SO ３ M ｅ 、 -R １２ｅ OSO ３ M ｅ 、 -OCO-R １２ｅ -COOM ｅ 、 -OCO-R １２ｅ -SO ３ M ｅ 、 -OCO-R １２ｅ -OSO ３ M ｅ 、 -COO-R １２ｅ -COOM ｅ 、 -COO-R １２ｅ -SO ３ M ｅ 、 -COO-R １２ｅ -OSO ３ M ｅ 、 -CONR ８ｅ -R １２ｅ -COOM ｅ 、 -CONR ８ｅ -R １２ｅ -SO ３ M ｅ 、 -CONR ８ｅ -R １２ｅ -OSO ３ M ｅ 、 -NR ８ｅ CO-R １２ｅ -COOM ｅ 、 -NR ８ｅ CO-R １２ｅ -SO ３ M ｅ 、 -NR ８ｅ CO-R １２ｅ -OSO ３ M ｅ 、 -OS(=O) ２ -R １２ｅ -COOM ｅ 、 -OS(=O) ２ -R １２ｅ -SO ３ M ｅ 、 or -OS(=O) ２ -R １２ｅ -OSO ３ Mｅ (In the formula, R ８ｅ and M ｅ is as above. １２ｅ is C １－１０ The alkylene group represented by the formula (I) is preferred. １２ｅ In the alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0511] General formula: -Y ｅ -R ６ｅ Examples of the group represented by the general formula: -R １０ｅ -CO-R １１ｅ A group represented by the general formula: -OCO-R １０ｅ -CO-R １１ｅ A group represented by the general formula: -COO-R １０ｅ -CO-R １１ｅ A group represented by the general formula: -OCO-R １０ｅ -COO-R １１ｅ A group represented by the general formula: -COO-R １１ｅ A group represented by the general formula: -NR ８ｅ CO-R １０ｅ -CO-R １１ｅ or a group represented by the general formula: -CONR ８ｅ -R １０ｅ -NR ８ｅ CO-R １１ｅ (wherein R ８ｅ , R １０ｅ and R １１ｅ is as described above.) is preferred.

[0512] In the formula, R ４ｅ and R ５ｅ is independently H or C １－４ The alkyl group represented by the formula R ４ｅ and R ５ｅThe alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0513] R in general formula (e-1) ３ｅ is H or optionally substituted C １－２０ The alkyl group is preferably H or unsubstituted C １－２０ The alkyl group represented by the formula (I) is more preferred, and H is even more preferred. ３ｅ The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0514] R in general formula (e-3) ２ｅ is H, OH or optionally substituted C １－２０ The alkyl group having no H, OH or substituent is preferably C １－２０ The alkyl group represented by the formula (I) is more preferred, and H or OH is even more preferred. ２ｅ The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0515] The surfactant (e) can be produced by a known production method.

[0516] The specific hydrocarbon surfactant is also preferably a carboxylic acid hydrocarbon surfactant. The carboxylic acid hydrocarbon surfactant is not limited as long as it has a carboxy group (-COOH) or a group in which the hydrogen atom of the carboxy group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.). For example, from the specific hydrocarbon surfactants described above, a hydrocarbon surfactant having a carboxy group or a group in which the hydrogen atom of the carboxy group is substituted with an inorganic cation can be used. In the carboxylic acid hydrocarbon surfactant, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0517] The carboxylic acid type hydrocarbon surfactant is preferably 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), which has a carboxy group (—COOH) or a group in which the hydrogen atom of the carboxy group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.).

[0518] The specific hydrocarbon surfactant is also preferably a sulfonic acid hydrocarbon surfactant. ３ H group, -OSO ３ There are no particular limitations on the surfactants as long as they have an H group or a group in which the hydrogen atom of such a group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.), and examples thereof include, from the specific hydrocarbon surfactants described above, -SO ３ H group, -OSO ３ Hydrocarbon surfactants having an H group or a group in which the hydrogen atoms of these groups have been substituted with inorganic cations can be used. In the sulfonic acid hydrocarbon surfactant, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms at all).

[0519] The TFE polymer composition of the present disclosure can be produced efficiently by using at least one of the above-mentioned specific hydrocarbon surfactants.In addition, the TFE polymer composition of the present disclosure can be produced by simultaneously using two or more of the above-mentioned specific hydrocarbon surfactants, or can be produced by simultaneously using other surfactant compounds other than the above-mentioned specific hydrocarbon surfactants, as long as they have volatility or can remain in the molded article etc. that is made of TFE polymer.

[0520] As the other compounds having surface activity, for example, those described in JP-T-2013-542308, JP-T-2013-542309, and JP-T-2013-542310 can be used.

[0521] The other surfactant compounds may be surfactants having a hydrophilic portion and a hydrophobic portion on the same molecule, such as hydrocarbon surfactants. These may be cationic, nonionic, or anionic. In the above compounds, the ratio of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0522] Cationic surfactants typically have a positively charged hydrophilic portion, such as an alkylated ammonium halide, such as an alkylated ammonium bromide, and a hydrophobic portion, such as a long-chain fatty acid. In the cationic surfactant, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0523] Anionic surfactants typically have a hydrophilic portion such as a carboxylate, sulfonate, or sulfate, and a hydrophobic portion that is a long-chain hydrocarbon portion such as an alkyl. In the anionic surfactant, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0524] Nonionic surfactants generally do not contain charged groups and have a hydrophobic portion that is a long hydrocarbon chain. The hydrophilic portion of the nonionic surfactant contains a water-soluble functional group, such as an ethylene ether chain derived from polymerization with ethylene oxide. In the nonionic surfactant, the proportion of hydrogen atoms bonded to carbon atoms that are substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0525] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

[0526] Specific examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene behenyl ether.

[0527] Specific examples of polyoxyethylene alkylphenyl ethers include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0528] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.

[0529] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0530] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0531] Specific examples of glycerol esters include glycerol monomyristate, glycerol monostearate, and glycerol monooleate.

[0532] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

[0533] The ethers and esters may have an HLB value of 10-18.

[0534] 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.), and Tergitol (registered trademark) L series, all manufactured by Dow Chemical Company; and Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m to 22, n to 23)) and Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10), all manufactured by BASF.

[0535] Examples of anionic hydrocarbon surfactants include Versatic (registered trademark) 10 manufactured by Resolution Performance Products, and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0536] Other compounds having surface activity 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 R has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may form a ring; L is -ArSO ３ － , -SO ３ － , -SO ４ -, -PO ３ － or -COO － and M is H, a metal atom, or NR ５ ４ (R ５ may be the same or different and are H or an organic group (preferably an organic group not containing fluorine)), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. ３ － is an aryl sulfonate. ５ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Specifically, CH ３ - (CH ２ ) ｎ -LM (wherein n is an integer of 6 to 17, and L and M are the same as above). Mixtures in which R is an alkyl group having 12 to 16 carbon atoms and L-M is sulfate or sodium dodecyl sulfate (SDS) can also be used. Other surfactant compounds include those represented by R ６ (-L-M) ２ (In the formula, 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 the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. ３ － , -SO ３－ , -SO ４ -, -PO ３ － or -COO － and M is H, a metal atom, or NR ５ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ５ is H or an organic group (preferably an organic group not containing fluorine), -ArSO ３ － is an aryl sulfonate. ) Other examples of compounds having surface activity include anionic surfactants represented by the formula: R ７ (-L-M) ３ (In the formula, R ７ is a linear or branched alkylidyne group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylidyne group having 3 or more carbon atoms which may have a substituent, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. ３ － , -SO ３ － , -SO ４ -, -PO ３ － or -COO － and M is H, a metal atom, or NR ５ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ５ is H or an organic group (preferably an organic group not containing fluorine). ３ － is an aryl sulfonate.

[0537] 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 comprises a distinct hydrophobic portion and a hydrophilic portion. The hydrophobic portion comprises one or more dihydrocarbylsiloxane units, in which the substituents on the silicone atoms are entirely hydrocarbon. These siloxane surfactants can also be considered hydrocarbon surfactants in the sense that the carbon atoms of the hydrocarbyl groups are entirely substituted with hydrogen atoms, although these may be substituted with halogens such as fluorine; that is, the monovalent substituents on the carbon atoms of the hydrocarbyl groups are hydrogen. In the above siloxane surfactants, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is preferably 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (no substitution with fluorine atoms).

[0538] Siloxane hydrocarbon surfactants are also disclosed in US Pat. No. 6,841,616.

[0539] Siloxane-based anionic hydrocarbon surfactants include SilSense, available from Noveon® Consumer Specialties, a product of Lubrizol Advanced Materials, Inc. ＴＭ PE-100 silicone, SilSense ＴＭ CA-1 silicone and the like.

[0540] Examples of anionic hydrocarbon surfactants include the sulfosuccinate surfactant Lankropol (registered trademark) K8300 manufactured by Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate surfactants include diisodecyl sulfosuccinate sodium salt (Emulsogen (registered trademark) SB10 manufactured by Clariant) and diisotridecyl sulfosuccinate sodium salt (Polirol (registered trademark) TR / LNA manufactured by Cesapinia Chemicals).

[0541] Other surfactant compounds include PolyFox (registered trademark) surfactants manufactured by Omnova Solutions, Inc. ＴＭ PF-156A, PolyFox ＴＭ PF-136A, etc.)

[0542] The other surfactant compound is preferably an anionic hydrocarbon surfactant. As the anionic hydrocarbon surfactant, those described above can be used, but for example, the following hydrocarbon surfactants can be suitably used.

[0543] Examples of the anionic hydrocarbon surfactant include those represented by the following formula (α): １００ -COOM (α) (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 , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R １０１ R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. １０１ The organic group in R is preferably an alkyl group. １０１ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. １００ The number of carbon atoms in R is preferably 2 or more, and more preferably 3 or more. １００ The number of carbon atoms in is preferably 29 or less, more preferably 23 or less. The metal atom of M includes alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. M is H, a metal atom, or NR １０１ ４ is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR １０１４ is more preferred, and H, Na, K, Li or NH ４ is more preferred, Na, K or NH ４ is even more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred.

[0544] The compound (α) may be R １０２ -COOM (in the formula, R １０２ is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the carbon number is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above. ) are also included. Specifically, CH ３ - (CH ２ ) ｎ -COOM (wherein n is an integer of 2 to 28, and M is the same as above).

[0545] From the viewpoint of emulsion stability, the compound (α) may be one that does not contain a carbonyl group (excluding the carbonyl group in the carboxy group). Examples of the hydrocarbon-containing surfactant that does not contain a carbonyl group include those represented by the following formula (A1): １０３ -COO-M (A1) (wherein, R １０３ is an alkyl group, an alkenyl group, an alkylene group, or an alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond; M is H, a metal atom, NR １０１ ４ , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. １０１ are the same or different and are H or an organic group (preferably an organic group not containing fluorine). １０３is preferably an alkyl group or an alkenyl group (which may contain an ether group). １０３ The alkyl group or alkenyl group in the above R may be linear or branched. １０３ The number of carbon atoms is not limited, but is, for example, 2 to 29.

[0546] When the alkyl group is linear, R １０３ The number of carbon atoms in R is preferably 3 to 29, and more preferably 5 to 23. When the alkyl group is branched, R １０３ The number of carbon atoms in R is preferably 5 to 35, and more preferably 11 to 23. When the alkenyl group is linear, R １０３ The number of carbon atoms in R is preferably 2 to 29, and more preferably 9 to 23. When the alkenyl group is branched, R １０３ The number of carbon atoms in the alkyl group is preferably 2 to 29, and more preferably 9 to 23.

[0547] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, and a vinyl group.

[0548] 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, and myristoleic acid. Examples of suitable salts include palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, osbondo acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, herring acid, and salts thereof. Particularly preferred are at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof. The salts include those in which the hydrogen atom of the carboxyl group is bonded to a metal atom of the formula M, NR １１ ４ Examples of the compound include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, and phosphonium which may have a substituent.

[0549] The anionic hydrocarbon surfactant may also be, for example, a surfactant represented by the following formula (β): １００ -SO ３ M (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 , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R １０１R is H or an organic group (preferably an organic group not containing fluorine), and may be the same or different. １０１ The organic group in R is preferably an alkyl group. １０１ is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. １００ The number of carbon atoms in R is preferably 2 or more, and more preferably 3 or more. １００ The number of carbon atoms in is preferably 29 or less, more preferably 23 or less. The metal atom of M includes alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. M is H, a metal atom, or NR １０１ ４ is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR １０１ ４ is more preferred, and H, Na, K, Li or NH ４ is more preferred, Na, K or NH ４ is even more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred.

[0550] The compound (β) includes R １０２ -SO ３ M (wherein, R １０２ is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the carbon number is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above. ) are also included. Specifically, CH ３ - (CH ２ ) ｎ -SO ３ M (wherein n is an integer of 2 to 28; M is the same as above).

[0551] From the viewpoint of emulsion stability, the compound (β) may not contain a carbonyl group (excluding the carbonyl group in the carboxy group). Examples of the hydrocarbon-containing surfactant not containing a carbonyl group include those represented by the following formula (B1): １０３ -SO ３ -M (B1) (wherein, R １０３ is an alkyl group, an alkenyl group, an alkylene group, or an alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond; M is H, a metal atom, NR １０１ ４ , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. １０１ are the same or different and are H or an organic group (preferably an organic group not containing fluorine). １０３ is preferably an alkyl group or an alkenyl group (which may contain an ether group). １０３ The alkyl group or alkenyl group in the above R may be linear or branched. １０３ The number of carbon atoms is not limited, but is, for example, 2 to 29.

[0552] When the alkyl group is linear, R １０３ The number of carbon atoms in R is preferably 3 to 29, and more preferably 5 to 23. When the alkyl group is branched, R １０３ The number of carbon atoms in R is preferably 5 to 35, and more preferably 11 to 23. When the alkenyl group is linear, R １０３ The number of carbon atoms in R is preferably 2 to 29, and more preferably 9 to 23. When the alkenyl group is branched, R １０３ The number of carbon atoms in the alkyl group is preferably 2 to 29, and more preferably 9 to 23.

[0553] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, and a vinyl group.

[0554] Examples of the compound (β) include aliphatic, unsaturated aliphatic, and aromatic sulfonic acids, aliphatic, unsaturated aliphatic, and aromatic sulfates, and salts thereof. Examples of the sulfonic acids include 1-hexanesulfonic acid, 1-octane sulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, perfluorobutanesulfonic acid, linear alkylbenzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, DBS, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, and butylnaphthalenesulfonic acid. Examples of the sulfates include sodium alkyl sulfates, alpha-sulfofatty acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alpha-olefin sulfonates, lauryl sulfate, myristyl sulfate, laureth sulfate, and polyoxyethylene alkylphenol sulfonic acid. As the compound (β), at least one selected from the group consisting of saturated aliphatic and aromatic sulfate esters and their salts is particularly preferred, and at least one selected from the group consisting of sodium alkyl sulfate esters, alpha-sulfofatty acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alpha-olefin sulfonates, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid, and their salts is more preferred. As the salt, a compound in which the hydrogen of the sulfonic acid group is bonded to a metal atom of the above-mentioned formula M, NR １１ ４ Examples of the compound include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, and phosphonium which may have a substituent.

[0555] The anionic hydrocarbon surfactant may be a surfactant represented by the following formula (1-0A): (In the formula, R １Ａ ~R ５Ａ represents H, a monovalent hydrocarbon group which may contain an ester group between carbon atoms, or a group represented by the general formula: -X Ａ -A, where R ２Ａ and R５Ａ At least one of the following is a general formula: -X Ａ represents a group represented by -A. Ａ A is the same or different in each occurrence and is a divalent hydrocarbon group or a bond; A is the same or different in each occurrence and is -COOM (M is H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ is H or an organic group (preferably an organic group not containing fluorine); R １Ａ ~R ５Ａ Any two of these may be bonded to each other to form a ring.

[0556] In general formula (1-0A), R １Ａ ~R ５Ａ In the formula (R), the number of carbon atoms in the monovalent hydrocarbon group, which may contain an ester group between carbon atoms, is preferably 1 to 50, and more preferably 5 to 20. １Ａ ~R ５Ａ Any two of these may be bonded to each other to form a ring. The monovalent hydrocarbon group which may contain an ester group between carbon atoms is preferably an alkyl group. Ａ In the formula (I), the number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 50, and more preferably 5 to 20. Examples of the divalent hydrocarbon group include an alkylene group and an alkanediyl group, with an alkylene group being preferred.

[0557] In general formula (1-0A), R ２Ａ and R ５Ａ Any one of the above general formula: -X Ａ -A is preferred, and R ２Ａ is represented by the above general formula: -X Ａ A group represented by -A is more preferred.

[0558] In the general formula (1-0A), R ２Ａ is represented by the general formula: -X Ａ -A, and R １Ａ , R３Ａ , R ４Ａ and R ５Ａ is H. In this case, X Ａ is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0559] In the general formula (1-0A), a preferred embodiment is also R ２Ａ is represented by the general formula: -X Ａ -A, and R １Ａ and R ３Ａ Ga-Y Ａ -R ６ and Y Ａ are the same or different in each occurrence and are —COO—, —OCO—, or a bond; R ６ In this embodiment, R is the same or different in each occurrence and is an alkyl group having 2 or more carbon atoms. ４Ａ and R ５Ａ is preferably H.

[0560] Examples of hydrocarbon surfactants represented by general formula (1-0A) include glutaric acid or a salt thereof, adipic acid or a salt thereof, pimelic acid or a salt thereof, suberic acid or a salt thereof, azelaic acid or a salt thereof, and sebacic acid or a salt thereof. The aliphatic carboxylic acid hydrocarbon surfactant represented by general formula (1-0A) may also be a two-chain two-hydrophilic group synthetic surfactant, such as Gemini surfactants, such as Geminisurf (Chukyo Yushi Co., Ltd.), Gemsurf α142 (12 carbon atoms, lauryl group), Gemsurf α102 (10 carbon atoms), and Gemsurf α182 (14 carbon atoms).

[0561] The anionic hydrocarbon surfactant may be a surfactant represented by the following formula I: R-(XZ) ｎ (I) wherein R is a hydrophobic hydrocarbon moiety containing one or more saturated or unsaturated, acyclic or cyclic aliphatic groups. ３ , C.H. ２ and CH relative to the total of CH groups ３The total percentage of groups is at least about 70%, and the hydrophobic moiety does not include a siloxane unit. Each X, which may be the same or different, represents an ionic hydrophilic moiety. Each Z, which may be the same or different, represents one or more counterions of the ionic hydrophilic moiety. n is 1 to 3.

[0562] Compound I exhibits low reactivity with polymerization initiators and / or propagating fluoropolymer radicals in emulsion polymerization of fluoromonomers.

[0563] Compound I has the following formula: (In the formula, Y ＋ is hydrogen, ammonium, quaternary ammonium, a nitrogen heterocycle, an alkali metal, or an alkaline earth metal.

[0564] Compound I has the following formula II: (In the formula, R ２’ and R ２’’’ are the same or different and are saturated or unsaturated, acyclic or cyclic aliphatic groups having 4 to 16 carbon atoms; R ２’ and R ２’’’ CH in the group ３ , C.H. ２ and CH relative to the total of CH groups ３ The total percentage of groups is at least about 70%, or R ２’ and R ２’’’ may be joined together to form a saturated or unsaturated aliphatic ring which may contain ether or ester bonds, provided that the CH ３ , C.H. ２ and CH relative to the total of CH groups ３ The total percentage of R groups is at least about 70%. １ is hydrogen, methoxy, ethoxy or phenoxy. ＋ is hydrogen, ammonium, quaternary ammonium, a nitrogen heterocycle, an alkali metal, or an alkaline earth metal.

[0565] As Compound II, for example, the following compounds are preferred. Y in the above formula ＋may be hydrogen, ammonium, or an alkali metal.

[0566] Compound I has the following formula III: (In the formula, R ３ , R ４’ , and R ４’’ are the same or different and are hydrogen or a saturated or unsaturated, acyclic or cyclic aliphatic group having 4 to 16 carbon atoms; R ３ , R ４’ , and R ４’’ CH in the group ３ , C.H. ２ and CH for the sum of CH groups ３ The total percentage of R is at least about 70%. ３ , R ４’ , and R ４’’ At least one of R is not hydrogen; ４’ and R ４’’ is hydrogen, R ３ is not hydrogen, but R ３ is hydrogen, R ４’ and R ４’’ is not hydrogen. ＋ is hydrogen, ammonium, quaternary ammonium, a nitrogen heterocycle, an alkali metal, or an alkaline earth metal.

[0567] As the compound III, for example, the following compounds are preferred. Y in the above formula ＋ may be hydrogen, ammonium, or an alkali metal.

[0568] Even if the TFE polymer composition of the present disclosure does not use the above-mentioned specific hydrocarbon surfactant, it can be obtained by a production method comprising the polymerization step of obtaining TFE polymer by polymerizing only tetrafluoroethylene or tetrafluoroethylene and the modified monomer copolymerizable with the above-mentioned tetrafluoroethylene in an aqueous medium with pH 4.0 or more in the presence of hydrocarbon surfactant and polymerization initiator.Conventionally, the polymerization step for producing TFE polymer has used an acidic polymerization initiator, so the pH of the aqueous medium used in polymerization is less than 4.0.Through intensive research, the present inventors have unexpectedly found that by making the pH of the aqueous medium used for polymerization 4.0 or more, the stability of polymerization can be improved, and the TFE polymer with high molecular weight can be produced.The above-mentioned production method comprises the polymerization of only tetrafluoroethylene or tetrafluoroethylene and the modified monomer copolymerizable with the above-mentioned tetrafluoroethylene in an aqueous medium with pH 4.0 or more. The pH may be 4.0 or higher, preferably greater than 4.0, more preferably 4.5 or higher, even more preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, particularly preferably 6.5 or higher, particularly preferably 7.0 or higher, particularly preferably 7.5 or higher, and particularly preferably 8.0 or higher. The upper limit of the pH is not particularly limited, but may be, for example, 13.0 or lower. From the viewpoint of corrosion of the polymerization vessel, it is preferably 12.0 or lower, more preferably 11.5 or lower, and even more preferably 11.0 or lower. The pH can be measured using a pH meter.

[0569] In the above-mentioned production method, the method for adjusting the pH of the aqueous medium to 4.0 or more is not particularly limited, and for example, the pH can be adjusted to 4.0 or more by using an alkaline aqueous solution, an alkaline aqueous dispersion, or a pH adjuster, but is not particularly limited. Furthermore, even when a polymerization initiator that is acidic when dissolved in an aqueous medium is used, the pH can also be adjusted to 4.0 or more by further adding an alkaline compound such as sodium hydroxide. The alkaline compound is, for example, an alkaline compound that dissolves in water and ionizes to form OH. －Any compound capable of generating the above-mentioned polymerization reaction may be used, and examples thereof include, but are not limited to, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc. The polymerization step may include a step of adding an alkali compound to the aqueous medium.

[0570] In the above production method, the pH of the aqueous medium may be 4.0 or higher throughout the entire polymerization step. Alternatively, the pH may be 4.0 or higher in the middle of the polymerization step, or in the latter half of the polymerization step. Alternatively, the pH may be 4.0 or higher in both the middle and latter half of the polymerization step.

[0571] In the polymerization step, the polymer solids concentration is 3% by mass (preferably 5% by mass, more preferably 8% by mass, even more preferably 10% by mass, even more preferably 15% by mass, especially more preferably 18% by mass, especially even more preferably 20% by mass, particularly preferably 25% by mass). From the start of polymerization, the polymer solids concentration is 10% by mass (preferably 8% by mass, more preferably 5% by mass, even more preferably 10% by mass, even more preferably 15% by mass, especially even more preferably 18% by mass, especially even more preferably 20% by mass, particularly preferably 25% by mass). The pH of the aqueous medium is preferably 4.0 or higher for a period of 60% or more (preferably 70% by mass, more preferably 80% by mass, even more preferably 90% by mass, even more preferably 95% by mass, especially even more preferably 99% by mass, particularly preferably 100%). In the polymerization step, the polymer solids concentration is 10% by mass (preferably 8% by mass, more preferably 5% by mass, even more preferably 3% by mass, even more preferably polymerization start). From the start of polymerization, the polymer solids concentration is 15% by mass. ... preferably 15% by mass. From the start of polymerization, the polymer solids concentration is preferably 15% by mass. In the polymerization step, the polymer solids concentration is 15% by mass, and the polymer solids concentration is 18% by mass (preferably 20% by mass, more preferably 25% by mass). The pH of the aqueous medium is preferably 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, especially more preferably 99% or more, particularly preferably 100%). In the polymerization step, the polymer solids concentration is 25% by mass (preferably 20% by mass, more preferably 18% by mass, even more preferably 15% by mass, even more preferably 10% by mass, especially more preferably 8% by mass, especially preferably 5% by mass, more preferably 3% by mass, even more preferably polymerization start). The pH of the aqueous medium is preferably 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, more preferably 99% or more, particularly preferably 100%).In any case, the pH of the aqueous medium is preferably greater than 4.0, more preferably 4.5 or more, even more preferably 5.0 or more, even more preferably 5.5 or more, particularly preferably 6.0 or more, particularly preferably 6.5 or more, more preferably 7.0 or more, even more preferably 7.5 or more, and even more preferably 8.0 or more.

[0572] In the above-mentioned production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, and is preferably an anionic hydrocarbon surfactant, more preferably a carboxylic acid hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid hydrocarbon surfactant are not particularly limited, but for example, the compound (α) exemplified among the above-mentioned other compounds having surface activity can be suitably used.

[0573] In the above-mentioned production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and also preferably a sulfonic acid hydrocarbon surfactant. The anionic hydrocarbon surfactant and the sulfonic acid hydrocarbon surfactant are not particularly limited. For example, the compound (β) exemplified among the above-mentioned other compounds having surface activity can be suitably used.

[0574] Even if the TFE polymer composition of the present disclosure does not use the above-mentioned specific hydrocarbon surfactant, it comprises a polymerization step of obtaining a TFE polymer by polymerizing tetrafluoroethylene alone or tetrafluoroethylene and the modified monomer copolymerizable with the above-mentioned tetrafluoroethylene in an aqueous medium in the presence of anionic hydrocarbon surfactant and polymerization initiator, and the hydrocarbon surfactant comprises the 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.Through intensive research, the present inventors have unexpectedly found that by the anionic hydrocarbon surfactant containing the salt of anionic hydrocarbon surfactant, the stability of polymerization is improved, and a TFE polymer with a large molecular weight can be produced.The anionic hydrocarbon surfactant will be described later.The fact that the anionic hydrocarbon surfactant contains the salt of the hydrocarbon surfactant can be confirmed by measuring electrical conductivity. In the above-mentioned production method, the concentration of the salt of the anionic hydrocarbon surfactant is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of the anionic hydrocarbon surfactant. The proportion of the salt can be measured by the solution concentration and conductivity. In the above-mentioned production method, the hydrocarbon surfactant is more preferably a carboxylic acid-type hydrocarbon surfactant. The hydrocarbon surfactant does not contain fluorine. In the salt of the anionic hydrocarbon surfactant, the cation (excluding hydrogen atoms) replacing the hydrogen atom of the acid can be, for example, a metal atom, NR ｙ ４ (R ｙ may be the same or different and are 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. ｙis preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. The cation in the salt of the anionic hydrocarbon surfactant may be a metal atom or NR ｙ ４ is preferred, and NR ｙ ４ is more preferred, and NH ４ Since the conductivity is greatly affected by temperature, the temperature of the sample liquid is kept at 25°C using a thermostatic bath, and the temperature of the pH meter cell is also kept at the same temperature before measuring the conductivity.

[0575] In the above production method, the polymerization step is preferably carried out substantially in the absence of the hydrocarbon surfactant in the form of an organic acid. By carrying out the polymerization substantially in the absence of the hydrocarbon surfactant in the form of an organic acid, the stability of the polymerization is further improved, and a high molecular weight TFE polymer can be obtained. "Substantially in the absence of the hydrocarbon surfactant in the form of an organic acid" means that the concentration of the organic acid is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, particularly preferably 0.05 mass% or less, and particularly preferably 0.01 mass% or less, relative to the mass of the obtained aqueous dispersion. In this specification, "organic acid" means an organic compound that exhibits acidity. Examples of organic acids include carboxylic acids having a -COOH group and -SO ３ Examples of suitable organic acids include sulfonic acids having a H group, and carboxylic acids are preferred because they allow for easy adjustment of the pH of an aqueous solution containing the organic acid. The term "organic acid form" refers to the acidic group (e.g., -COOH group, -SO ) contained in the organic acid. ３ In the above production method, the hydrocarbon surfactant is an anionic hydrocarbon surfactant.

[0576] In the above-mentioned polymerization process, the amount of hydrocarbon surfactant at the start of polymerization is preferably more than 50 ppm relative to aqueous medium.The amount of hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or more, more preferably 70 ppm or more, even more preferably 80 ppm or more, and even more preferably 100 ppm or more.The upper limit is not particularly limited, but for example, it is preferably 10000 ppm, more preferably 5000 ppm.By the amount of hydrocarbon surfactant at the start of polymerization being within the above range, it is possible to obtain an aqueous dispersion with a smaller average primary particle size and better stability.It can be said that polymerization begins when the gaseous TFE in the reactor becomes a TFE-based polymer and the pressure in the reactor drops.U.S. Pat. No. 3,391,099 (Punderson) discloses the dispersion polymerization of tetrafluoroethylene in aqueous medium, which comprises two separate stages of polymerization process: first, the formation of polymer nuclei as nucleation sites, and then the growth stage comprising the polymerization of established particles. It should be noted that polymerization typically begins when both the monomer to be polymerized and the polymerization initiator are charged into the reactor. In the present disclosure, an additive involved in the formation of nucleation sites is referred to as a nucleating agent.

[0577] The polymerization step preferably includes an addition step of adding a composition containing a hydrocarbon surfactant after the initiation of polymerization. This addition step further improves the stability of the polymerization, resulting in a TFE polymer with a higher molecular weight. The hydrocarbon surfactant may be, for example, in the form of a solid (e.g., a hydrocarbon surfactant powder) or a liquid. The composition may contain a hydrocarbon surfactant, and may consist solely 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 addition step can also be described as a step of adding a hydrocarbon surfactant alone or a composition containing a hydrocarbon surfactant after the initiation of polymerization. The hydrocarbon surfactant is not limited to one type, and may be a mixture of two or more types. The liquid medium may be either an aqueous medium or an organic solvent, or a combination of an aqueous medium and an organic solvent. Specific examples of the composition include an aqueous solution in which a hydrocarbon surfactant is dissolved in an aqueous medium, and an aqueous dispersion in which a hydrocarbon surfactant is dispersed in an aqueous medium.

[0578] The amount of the hydrocarbon surfactant added in the addition step is preferably 0.0001 to 10% by mass relative to the aqueous medium. It is more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more, relative to the aqueous medium. It is also more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less, relative to the aqueous medium.

[0579] The stability of polymerization is improved, and the TFE polymer of higher molecular weight can be obtained, so the above-mentioned composition preferably comprises hydrocarbon surfactant and is the aqueous solution of pH 5.0 or more.The pH of above-mentioned aqueous solution is more preferably 6.0 or more, more preferably 6.5 or more, more preferably 7.0 or more, particularly preferably 7.5 or more, particularly preferably 8.0 or more.In addition, the upper limit of pH is not particularly limited, but can be 12.0 or less, and can also be 11.0 or less.

[0580] The hydrocarbon surfactant used in the addition step is preferably an anionic hydrocarbon surfactant, more preferably a carboxylic acid type hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid type hydrocarbon surfactant are not particularly limited, but for example, the compound (α) exemplified among the above-mentioned other compounds having surface activity can be suitably used.

[0581] The carboxylic acid type hydrocarbon surfactant used in the polymerization step and the addition step includes the surfactant (e) and the surfactant of the above formula: R ６ (-L-M) ２ and anionic surfactants represented by the above formula: R ７ (-L-M) ３ Among the anionic surfactants represented by the formula: １０２ -COOM (in the formula, R １０２ and M are the same as above.), as well as anionic surfactants represented by the above formula: R-L-M (wherein R, L, and M are the same as above), and surfactants (c) and (d) above which have a carboxy group (—COOH) or a group in which a hydrogen atom of the carboxy group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.).

[0582] The carboxylic acid type hydrocarbon surfactant is preferably the compound (α), and is preferably a compound represented by the formula (A1), a compound represented by the formula (c), ｃ Ga-COOX ｃ a compound represented by the formula (d) ｄ Ga-COOXｄ a compound represented by the formula (e) ｅ Ga-COOM ｅ and at least one selected from the group consisting of a compound represented by the formula (1-0A) where A is -COOM, a compound represented by the formula (1-0A) where A is -COOM, and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment, and even more preferred is at least one selected from the group consisting of a compound represented by the formula (A1) and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment. In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, salts thereof, and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment is preferred. As the above salts, a compound in which the hydrogen of the carboxy group is bonded to a metal atom of the formula M, NR １０１ ４ Examples of the compound include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, and phosphonium which may have a substituent.

[0583] The above-mentioned production method is preferably one in which tetrafluoroethylene is polymerized substantially in the absence of a fluorine-containing surfactant.In the above-mentioned production method, "substantially in the absence of a fluorine-containing surfactant" means that the fluorine-containing surfactant is 10 mass ppm or less relative to the aqueous medium, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, even more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, even more preferably 1 mass ppb or less, particularly preferably less than 1 mass ppb."Substantially in the absence of a fluorine-containing surfactant" also means that no fluorine-containing surfactant is intentionally added.

[0584] Examples of the fluorine-containing surfactant include anionic fluorine-containing surfactants, etc. The anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less excluding the anionic group.

[0585] The fluorine-containing surfactant may also be a surfactant containing fluorine, the molecular weight of the anionic moiety of which is 1000 or less, preferably 800 or less. The "anionic moiety" means the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF) represented by the formula (I) described below may be used. ２ ) ｎ１ In the case of COOM, "F(CF ２ ) ｎ１ This is the "COO" part.

[0586] Specific examples of the fluorine-containing surfactants 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, and U.S. Patent No. 3,250,808. , U.S. Patent No. 3,271,341, JP 2003-119204 A, WO 2005 / 042593, WO 2008 / 060461, WO 2007 / 046377, WO 2007 / 119526, WO 2007 / 046482, WO 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, WO 2013 / 189824, and those described in WO 2013 / 189826, and the like.

[0587] The anionic fluorine-containing surfactant may be a compound represented by the general formula (N ０ ) is an example of a compound represented by the formula (I).

[0588] As described above, examples of the anionic fluorine-containing surfactant include carboxylic acid-based fluorine-containing surfactants and sulfonic acid-based fluorine-containing surfactants.

[0589] The TFE polymer composition of the present disclosure can be suitably produced by a production method comprising the addition step of adding at least one selected from the group consisting of radical scavengers and decomposers of polymerization initiators.The above-mentioned addition step is carried out during the step of carrying out the above-mentioned emulsion polymerization in an aqueous medium.By adding radical scavengers or decomposers of polymerization initiators, the radical concentration during polymerization can be adjusted.From the viewpoint of reducing radical concentration, radical scavengers are preferred.

[0590] The radical scavenger is a compound that does not have the ability to reinitiation after addition or chain transfer to the free radicals in the polymerization system. Specifically, a compound that easily undergoes chain transfer reaction with a primary radical or a propagating radical to generate a stable radical that does not subsequently react with the monomer, or a compound that easily undergoes an addition reaction with a primary radical or a propagating radical to generate a stable radical, is used. The activity of what is generally called a chain transfer agent is characterized by the chain transfer constant and the reinitiation efficiency, and among chain transfer agents, those with a reinitiation efficiency of almost 0% are called radical scavengers. The radical scavenger can also be described as, for example, a compound whose chain transfer constant with TFE at the polymerization temperature is greater than the polymerization rate constant and whose reinitiation efficiency is essentially 0%. "Reinitiation efficiency is essentially 0%" means that the generated radical turns the radical scavenger into a stable radical. Preferably, the compound has a chain transfer constant (Cs) (= chain transfer rate constant (kc) / polymerization rate constant (kp)) with TFE at polymerization temperature of more than 0.1, and the chain transfer constant (Cs) of the compound is more preferably 0.5 or more, even more preferably 1.0 or more, even more preferably 5.0 or more, and particularly preferably 10 or more.

[0591] Examples of the radical scavenger in the present disclosure include aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl ２) is preferred. Examples of aromatic hydroxy compounds include unsubstituted phenol, polyhydric phenol, salicylic acid, m- or p-salicylic acid, gallic acid, naphthol, etc. Examples of the unsubstituted phenol include o-, m-, or p-nitrophenol, o-, m-, or p-aminophenol, p-nitrosophenol, etc. Examples of polyhydric phenols include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, naphthresorcinol, etc. Examples of aromatic amines include o-, m-, or p-phenylenediamine, benzidine, etc. Examples of the quinone compounds include o-, m-, or p-benzoquinone, 1,4-naphthoquinone, alizarin, etc. Examples of thiocyanates include ammonium thiocyanate (NH ４ Examples of the radical scavenger include potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN), etc. Among these, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

[0592] From the viewpoint of reducing the standard specific gravity, the amount of radical scavenger added is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration. A more preferred lower limit is 5% (molar basis), even more preferably 8% (molar basis), even more preferably 10% (molar basis), even more preferably 15% (molar basis), especially even more preferably 20% (molar basis), particularly preferably 25% (molar basis), especially preferably 30% (molar basis), especially preferably 35% (molar basis). A more preferred upper limit is 400% (molar basis), even more preferably 300% (molar basis), even more preferably 200% (molar basis), especially even more preferably 100% (molar basis).

[0593] The polymerization initiator decomposer may be any compound capable of decomposing the polymerization initiator 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 preferred. Examples of sulfites include sodium sulfite and ammonium sulfite. Examples of copper salts include copper(II) sulfate, and examples of iron salts include iron(II) sulfate. The amount of the polymerization initiator decomposer added is in the range of 25 to 300% by mass relative to the amount of the oxidizing agent combined as the polymerization initiator (the redox initiator described below). This is preferably 25 to 150% by mass, more preferably 50 to 100% by mass. The amount of the polymerization initiator decomposer added is preferably an amount equivalent to 3 to 500% (molar basis) of the polymerization initiator concentration in order to reduce the standard specific gravity. A more preferred lower limit is 5% (molar basis), even more preferably 8% (molar basis), even more preferably 10% (molar basis), even more preferably 13% (molar basis), even more preferably 15% (molar basis).A more preferred upper limit is 400% (molar basis), even more preferably 300% (molar basis), even more preferably 200% (molar basis), and especially preferably 100% (molar basis).

[0594] At least one selected from the group consisting of radical scavengers and decomposers of polymerization initiators is preferably added when the concentration of the TFE-based polymer formed in the aqueous medium is 5% by mass or more, more preferably 10% by mass or more, and is preferably added when the concentration of the TFE-based polymer formed in the aqueous medium is 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0595] 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 a polymerization initiator. Continuously adding 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 over time, without interruption, or in portions, rather than all at once.

[0596] The polymerization step may further comprise polymerizing tetrafluoroethylene in the presence of a nucleating agent.

[0597] As the nucleating agent, for example, it is preferred to be at least one selected from the group consisting of fluoropolyether, nonionic surfactant and chain transfer agent.In this case, it is preferred that the polymerization step is the step of obtaining TFE polymer by polymerizing tetrafluoroethylene in aqueous medium under the presence of hydrocarbon surfactant and the nucleating agent.

[0598] The fluoropolyether is preferably a perfluoropolyether.

[0599] The fluoropolyether preferably has repeating units represented by formulas (1a) to (1d): (-CFCF ３ -CF ２ -O-) ｎ (1a) (-CF ２ -CF ２ -CF ２ -O-) ｎ (1b) (-CF ２ -CF ２ -O-) ｎ -(-CF ２ -O-) ｍ (1c) (-CF ２ -CFCF ３ -O-) ｎ -(-CF ２ -O-) ｍ (1d) (In formulas (1a) to (1d), m and n are integers of 1 or more.)

[0600] The fluoropolyether is preferably a fluoropolyether acid or its salt, and the fluoropolyether acid is preferably a carboxylic acid, a sulfonic acid, a sulfonamide, or a phosphonic acid, and more preferably a carboxylic acid. Among the fluoropolyether acids or their salts, the salt of a fluoropolyether acid is preferred, the ammonium salt of a fluoropolyether acid is more preferred, and the ammonium salt of a fluoropolyether carboxylic acid is even more preferred.

[0601] The fluoropolyether acids or salts thereof can have any chain structure in which the oxygen atoms in the backbone of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. More than one type of fluorocarbon group can be present in the molecule.

[0602] The fluoropolyether acid or salt thereof may be a fluoropolyether acid represented by the following formula: CF ３ -CF ２ -CF ２ -O(-CFCF ３ -CF ２ -O-) ｎ CFCF ３ -COOH, CF ３ -CF ２ -CF ２ -O(-CF ２ -CF ２ -CF ２ -O-) ｎ -CF ２ -CF ２ COOH or HOOC-CF ２ -O(-CF ２ -CF ２ -O-) ｎ -(-CF ２ -O-) ｍ CF ２ COOH (wherein m and n are the same as above) or a salt thereof is preferred.

[0603] These structures are discussed by Kasai in J. Appl. Polymer Sci., 57, 797 (1995). As disclosed therein, such fluoropolyethers can have a carboxylic acid group or its salt at one or both ends. Similarly, such fluoropolyethers can have a sulfonic acid or phosphonic acid group or its salt at one or both ends. In addition, fluoropolyethers with acid functional groups at both ends can have different groups at each end. For monofunctional fluoropolyethers, the other end of the molecule is usually perfluorinated, but may contain a hydrogen or chlorine atom.

[0604] Fluoropolyethers having acid groups at one or both ends have at least two ether oxygens, preferably at least four ether oxygens, and even more preferably at least six ether oxygens. Preferably, at least one of the fluorocarbon groups separating the ether oxygens, more preferably at least two of such fluorocarbon groups, has 2 or 3 carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. Also, preferably, the fluoropolyether has a total of at least 15 carbon atoms, and for example, the preferred minimum value of n or n + m in the above repeating unit structure is at least 5. Two or more fluoropolyethers having acid groups at one or both ends can be used in the method according to the present disclosure. Typically, unless special care is taken in the preparation of a single specific fluoropolyether compound, the fluoropolyether may contain multiple compounds in various proportions within the molecular weight range relative to the average molecular weight.

[0605] The fluoropolyether preferably has a number average molecular weight of 800 g / mol or more. Because the fluoropolyether acid or its salt may be difficult to disperse in an aqueous medium, the number average molecular weight is preferably less than 6000 g / mol. The fluoropolyether acid or its salt more preferably has a number average molecular weight of 800 to 3500 g / mol, and even more preferably 1000 to 2500 g / mol.

[0606] The amount of the fluoropolyether is preferably 5 to 3000 ppm, more preferably 5 to 2000 ppm, with a more preferred lower limit of 10 ppm and a more preferred upper limit of 100 ppm relative to the aqueous medium.

[0607] Examples of the nonionic surfactant as the nucleating agent include the nonionic surfactants described above, and preferably nonionic surfactants that do not contain fluorine. For example, the nonionic surfactant may be a nonionic surfactant represented by the following general formula (i): ３ -O-A １ -H (i) (wherein, R３ is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A １ is a polyoxyalkylene chain. ３ The number of carbon atoms in R is preferably 10 to 16, and more preferably 12 to 16. ３ When the carbon number of R is 18 or less, good dispersion stability of the aqueous dispersion is easily obtained. ３ If the carbon number of R exceeds 18, the flow temperature is high and it is difficult to handle. ３ If the number of carbon atoms is less than 8, the surface tension of the aqueous dispersion increases, and the permeability and wettability tend to decrease.

[0608] The polyoxyalkylene chain may be composed of oxyethylene and oxypropylene. It is a polyoxyalkylene chain having an average repeat number of 5 to 20 oxyethylene groups and an average repeat number of 0 to 2 oxypropylene groups, and is a hydrophilic group. The number of oxyethylene units may include either a broad or narrow unimodal distribution as is usually provided, or a broader or bimodal distribution obtained by blending. When the average repeat number of oxypropylene groups is greater than 0, the oxyethylene groups and oxypropylene groups in the polyoxyalkylene chain may be arranged in a block or random configuration. From the viewpoint of viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain having an average repeat number of 7 to 12 oxyethylene groups and an average repeat number of 0 to 2 oxypropylene groups is preferred. In particular, A １ When the number of oxypropylene groups is 0.5 to 1.5 on average, low foaming properties are favorable, and this is preferred.

[0609] More preferably, R ３ is (R')(R'')HC-, where R' and R'' are the same or different straight, branched, or cyclic alkyl groups having a total of at least 5, preferably 7 to 17, carbon atoms. Preferably, at least one of R' or R'' is a branched or cyclic hydrocarbon group.

[0610] Specific examples of the polyoxyethylene alkyl ether include C １３ H ２７-O-(C ２ H ４ O) １０ -H, C １２ H ２５ -O-(C ２ H ４ O) １０ -H, C １０ H ２１ CH (CH ３ ) CH ２ -O-(C ２ H ４ O) ９ -H, C １３ H ２７ -O-(C ２ H ４ O) ９ -(CH(CH ３ ) CH ２ O) -H,C １６ H ３３ -O-(C ２ H ４ O) １０ -H, HC(C ５ H １１ ) (C ７ H １５ )—O—(C ２ H ４ O) ９ -H, etc. Examples of commercially available polyoxyethylene alkyl ethers include Genapol X080 (product name, manufactured by Clariant), the Noigen TDS series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) such as Noigen TDS-80 (trade name), the Leocol TD series (manufactured by Lion Corporation) such as Leocol TD-90 (trade name), the Lionol (registered trademark) TD series (manufactured by Lion Corporation), the T-Det A series (manufactured by Harcros Chemicals) such as T-Det A138 (trade name), and the Tergitol (registered trademark) 15S series (manufactured by Dow).

[0611] Also preferred is an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 4 to about 18 ethylene oxide units, an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 6 to about 12 ethylene oxide units, or a mixture thereof. Nonionic surfactants of this type are also commercially available, for example, under the trade names TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (all manufactured by The Dow Chemical Company).

[0612] The hydrophobic group of the nonionic surfactant may be any of an alkylphenol group, a linear alkyl group, and a branched alkyl group. For example, a polyoxyethylene alkylphenyl ether-based nonionic compound may be, for example, a compound represented by the following general formula (ii): ４ -C ６ H ４ -O-A ２ -H (ii) (wherein, R ４ is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms, A ２ is a polyoxyalkylene chain. Specific examples of the polyoxyethylene alkylphenyl ether-based nonionic compounds include Triton (registered trademark) X-100 (product name, manufactured by Dow Chemical Company).

[0613] Other nonionic surfactants include difunctional block copolymers supplied by BASF as their Pluronic® R series...

Claims

1. A tetrafluoroethylene-based polymer composition used as a binder for electrochemical devices, in which the number of carboxyl groups is 10 and the number of carbon atoms in the main chain is 10. ６ A tetrafluoroethylene-based polymer composition comprising no more than four tetrafluoroethylene-based polymers per particle.

2. The number of carboxyl groups in the tetrafluoroethylene polymer is 10. ６ 2. The tetrafluoroethylene polymer composition according to claim 1, wherein the number of units per unit area is 2 or less.

3. The tetrafluoroethylene polymer composition according to claim 1 or 2, which has a standard specific gravity of 2.130 or more and 2.180 or less.

4. The tetrafluoroethylene polymer composition according to any one of claims 1 to 3, 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 a carboxyl group number of 10 carbon atoms in the main chain. ６ A binder for electrochemical devices comprising a tetrafluoroethylene-based polymer having four or less molecules per particle.

6. The number of carboxyl groups in the tetrafluoroethylene polymer is 10. ６ 6. The binder for electrochemical devices according to claim 5, wherein the number of particles per one piece is two or less.

7. The binder for electrochemical devices according to claim 5 or 6, wherein the tetrafluoroethylene polymer composition has an endothermic peak temperature of 333°C or higher and 350°C or lower.

8. The binder for electrochemical devices according to any one of claims 5 to 7, wherein the tetrafluoroethylene polymer composition has a fibrillating ability.

9. The binder for electrochemical devices according to any one of claims 5 to 8, wherein the standard specific gravity of the tetrafluoroethylene polymer composition is 2.280 or less.

10. The binder for electrochemical devices according to any one of claims 5 to 9, wherein the standard specific gravity of the tetrafluoroethylene polymer composition is 2.130 or more and 2.180 or less.

11. The binder for electrochemical devices according to any one of claims 5 to 10, which is a binder for lithium ion secondary batteries and is in the form of a powder.

12. An electrode mixture comprising the tetrafluoroethylene polymer composition according to any one of claims 1 to 4 or the binder for electrochemical devices according to any one of claims 5 to 11, and an electrode active material.

13. The electrode mixture according to claim 12, which is in the form of a sheet.

14. An electrode comprising the tetrafluoroethylene polymer composition according to any one of claims 1 to 4, or the binder for electrochemical devices according to any one of claims 5 to 11, an electrode active material, and a current collector.

15. A secondary battery comprising the electrode according to claim 14.

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