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

Abstract

To provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device capable of improving the cycle characteristics of the electrochemical device and suppressing gas generation, and to provide a binder for the electrochemical device, an electrode mixture, an electrode, and a secondary battery, all using the same.SOLUTION: The tetrafluoroethylene-based polymer composition for use in a binder for an electrochemical device contains a tetrafluoroethylene-based polymer having a carboxyl group number of four or less per 106 carbon atoms in the main chain.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

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

[0004] Patent Documents 2 to 6 describe using polytetrafluoroethylene as a binder for a battery.

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

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0007] The present disclosure aims to provide a tetrafluoroethylene-based polymer composition for a binder for an electrochemical device, which can improve the cycle characteristics of the electrochemical device and suppress gas generation, and a binder for an electrochemical device, an electrode binder, an electrode, and a secondary battery using the same. [Means for Solving the Problems]

[0008] The present disclosure (1) is a tetrafluoroethylene-based polymer composition used for a binder for an electrochemical device, which is a tetrafluoroethylene-based polymer composition containing a tetrafluoroethylene-based polymer having 4 or less carboxyl groups per 10 main chain carbon atoms. 6 per 10 main chain carbon atoms.

[0009] The present disclosure (2) is the tetrafluoroethylene-based polymer composition according to the present disclosure (1), wherein the number of carboxyl groups of the tetrafluoroethylene-based polymer is 2 or less per 10 main chain carbon atoms. 6 per 10 main chain carbon atoms.

[0010] The present disclosure (3) is the tetrafluoroethylene-based polymer composition according to the present disclosure (1) or (2), having 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 described in any one of the present disclosures (1) to (3) which is used as a binder for a lithium ion secondary battery and is in powder form.

[0012] The present disclosure (5) is a binder for an electrochemical device consisting essentially of only a tetrafluoroethylene-based polymer composition, wherein the tetrafluoroethylene-based polymer composition has a carboxyl group number of 4 or less per 10 main chain carbon atoms. 6 It is a binder for an electrochemical device containing a tetrafluoroethylene-based polymer.

[0013] The present disclosure (6) is the binder for an electrochemical device according to the present disclosure (5), wherein the number of carboxyl groups of the tetrafluoroethylene-based polymer is 2 or less per 10 main chain carbon atoms. 6

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

[0015] The present disclosure (8) is the binder for an electrochemical device 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 an electrochemical device 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 an electrochemical device according to any one of the present disclosures (5) to (9), wherein the standard specific gravity of the tetrafluoroethylene-based polymer composition is 2.130 or higher and 2.180 or lower.

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

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

[0020] The present disclosure (13) is the electrode binder described in the present disclosure (12) which is a sheet.

[0021] The present disclosure (14) is an electrode containing a tetrafluoroethylene-based polymer composition described in any one of the present disclosures (1) to (4), or a binder for an electrochemical device described in 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 including the electrode described in the present disclosure (14).

Advantages of the Invention

[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 the electrochemical device and suppress gas generation, and a binder for an electrochemical device, an electrode binder, an electrode, and a secondary battery using the same.

Embodiments for Carrying Out the Invention

[0024] In the present disclosure, the "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. As the above organic group, an alkyl group which may have one or more substituents is preferable.

[0025] Hereinafter, the present disclosure will be specifically described.

[0026] The present disclosure is a tetrafluoroethylene (TFE)-based polymer composition used as a binder for an electrochemical device, and the number of carboxyl groups is 10 with respect to the number of main chain carbon atoms6 Provided is a TFE-based polymer composition containing a TFE-based polymer having 4 or less carboxyl groups per molecule.

[0027] By having the above configuration, the TFE-based polymer composition of the present disclosure can improve the cycle characteristics of an electrochemical device and suppress gas generation when used as a binder for an electrochemical device. In addition, the ionic conductivity of the electrochemical device can also be improved. Further, the amount of hydrogen fluoride eluted is small, oxidation of the metal members (such as an outer can) of the electrochemical device can be suppressed, and a decrease in electrical characteristics can be suppressed. Also, a composite sheet excellent in strength and flexibility can be obtained. Since the TFE-based polymer composition of the present disclosure can be used dry, it is not necessary to use a large amount of a dispersion medium such as water or an organic solvent, and a wide variety of electrode active materials and solid electrolytes to be combined can be selected, which is advantageous in terms of the production process. Also, the processes and costs due to the use of a dispersion medium can be reduced. Furthermore, since the TFE-based polymer composition of the present disclosure has excellent adhesion to an active material and an electrolyte, the amount used can be reduced.

[0028] In the TFE-based polymer in the TFE-based polymer composition of the present disclosure, the number of carboxyl groups is 4 or less per 10 main chain carbon atoms 6 However, in terms of further improving battery characteristics (cycle characteristics, gas generation amount, ionic conductivity, etc.), the number of carboxyl groups is preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, and particularly preferably 0.

[0029] In the TFE-based polymer in the TFE-based polymer composition of the present disclosure, in terms of further improving battery characteristics, the number of sulfonic acid groups is preferably 4 or less per 10 main chain carbon atoms 6 per molecule, more preferably 3 or less, still more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0.

[0030] In the TFE-based polymer composition of the present disclosure, the TFE-based polymer is such that in terms of further improving battery characteristics, the number of oxygen-containing polar groups per 10 main-chain carbon atoms 6 is preferably 4 or less, more preferably 3 or less, still 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, -SO3X a , -SO2X a , -OSO2X a , -PO3X a , and -OX a (wherein X a is -H, a metal atom, -NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, an alkyl group, or a nitrile group. R 1 is H or an organic group.) Examples of the carbonyl group-containing group include -COOX a , -OCOX a (wherein X a is the same as above), a carbonate group, a haloformyl group, an acid anhydride residue, and an isocyanate group. It is preferable that the total number of these functional groups is within the above-described range.

[0032] X a is -H, a metal atom, -NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, an alkyl group, or a nitrile group. X a Examples of the metal atom in X include monovalent and divalent metal atoms, and include alkali metals (Group 1) or alkaline earth metals (Group 2), and specifically, Na, K, Li, etc. are exemplified. The four Rs 1 may be the same or different. R 1is 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. X a The number of carbon atoms of the alkyl group in is preferably 1 or more, preferably 10 or less, more preferably 6 or less, and still 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. X a is preferably -H, an alkali metal atom, NH4, an alkyl group, or a nitrile group, more preferably -H, an alkali metal atom, NH4, or an alkyl group, and still more preferably -H, an alkali metal atom, or NH4.

[0033] The identification and measurement of the number of each of the above functional groups can be carried out by infrared spectroscopy. Specifically, the number of functional groups is measured by the following method. First, the 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 the infrared absorption spectrum of the above TFE-based polymer, and a difference spectrum from a base spectrum that is completely fluorinated and has no functional groups is obtained. From the absorption peak of a specific functional group that appears in this difference spectrum, according to the following formula (A), the number of functional groups N per 1 × 10 6 carbon atoms in the above TFE-based polymer is calculated. N = I × K / t (A) I: Absorbance K: Correction coefficient t: Thickness of the film (mm)

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

[0035]

Table 1

[0036] In addition, the absorption frequencies of -CH2COF, -CH2COOH, -CH2COOCH3, and -CH2CONH2 are several tens of wavenumbers (cm -1 ) lower than the absorption frequencies of -COF, -COOHfree and -COOHbonded, -COOCH3, and -CONH2 shown in the table, respectively. Therefore, for example, the number of functional groups of -COF is the sum of the number of functional groups determined from the absorption peak at the absorption frequency of 1883 cm -1 attributed to -CF2COF and the number of functional groups determined from the absorption peak at the absorption frequency of 1840 cm -1 attributed to -CH2COF.

[0037] The above TFE-based polymer may be a high molecular weight TFE-based polymer, a low molecular weight TFE-based polymer, or a mixture thereof. In the case of a mixture of a high molecular weight TFE-based polymer and a low molecular weight TFE-based polymer, it is preferable that the high molecular weight TFE-based polymer is the main component. In the mixture, the fact that the high molecular weight TFE-based polymer is the main component can be confirmed by having endothermic peaks in the region (A) where the endothermic peak temperature is 324 °C or higher and less than 333 °C and the region (B) where it is 333 °C or higher and 350 °C or lower, and the intensity ratio represented by the intensity of the endothermic peak in the region (A) / the intensity of the endothermic peak in the region (B) being 0.05 or more and 3.50 or less.

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

[0039] The above high molecular weight TFE-based polymer preferably has an endothermic peak temperature of 333°C or higher and 350°C or lower, more preferably 336°C or higher, still more preferably 348°C or lower, and even more preferably 346°C or lower. The endothermic peak temperature of the TFE-based polymer is the temperature corresponding to the minimum point in the melting heat curve obtained by performing differential scanning calorimetry [DSC] at a heating rate of 10°C / min for a TFE-based polymer having no heating history at a temperature of 300°C or higher. When there are two or more minimum points in one melting peak, each is taken as the endothermic peak temperature.

[0040] The above high molecular weight TFE-based polymer is preferably non-melt processable. In this specification, being non-melt processable means that the melt flow rate (MFR) is less than 0.25 g / 10 min, preferably less than 0.10 g / 10 min, more preferably 0.05 g / 10 min or less, and even more preferably 0.01 g / 10 min or less. The above MFR is a value obtained as the mass (g / 10 min) of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2.095 mm and a length of 8 mm at 372°C under a load of 5 kg using a melt indexer in accordance with ASTM D1238.

[0041] The above low molecular weight TFE-based polymer preferably has a melt viscosity (complex viscosity) of 1.0×10 1 ~1.0×10 7 Pa·s at 380°C. The above melt viscosity is more preferably 1.0×10 2 Pa·s or higher, still more preferably 1.5×10 3 Pa·s or higher, particularly preferably 7.0×10 3 Pa·s or higher, and also more preferably 7.0×10 5 Pa·s or lower, still more preferably 3.0×10 5 Pa·s or lower, and particularly preferably 1.0×10 5 Pa·s or lower. The melt viscosity was 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 pre-heated at 380 °C for 5 minutes and maintained at the above temperature under a load of 0.7 MPa.

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

[0043] The low molecular weight TFE-based polymer is preferably melt processable. In this specification, being melt processable means that the melt flow rate (MFR) is 0.25 g / 10 min or more, preferably 0.50 g / 10 min or more, and more preferably 1.00 g / 10 min or more. The above MFR may be 100 g / 10 min or less, and preferably 80 g / 10 min or less.

[0044] The TFE-based polymer may be a homopolymer of TFE, or a TFE copolymer containing a polymerization unit based on TFE (TFE unit) and a polymerization unit based on a modified monomer copolymerizable with TFE (modified monomer unit). The TFE-based polymer may be polytetrafluoroethylene (PTFE). The above PTFE includes a homopolymer of TFE and a modified PTFE containing 99.0 mass% or more of TFE units and 1.0 mass% or less of modified monomer units. The TFE-based polymer is preferably PTFE and more preferably modified PTFE in terms of further improving battery characteristics. In the present disclosure, the homopolymer of TFE refers to a polymer in which the content of the modified monomer unit with respect to all polymerization units is less than 0.0001 mass%.

[0045] The content of the modified monomer unit is preferably in the range of 0.0001 to 10% by mass with respect to all polymerization units in terms of further improving battery characteristics. As the lower limit of the content of the modified monomer unit, 0.001% by mass is more preferable, 0.010% by mass is still more preferable, 0.015% by mass is even more preferable, and 0.020% by mass is particularly preferable. As the upper limit of the content of the modified monomer unit, 5.0% by mass is preferable, 3.0% by mass is more preferable, 1.0% by mass is still more preferable, 0.80% by mass is even more preferable, 0.60% by mass is even more preferable, 0.50% by mass is even more preferable, 0.40% by mass is even more preferable, 0.30% by mass is even more preferable, 0.20% by mass is even more preferable, and 0.10% by mass is particularly preferable. In this specification, the above-mentioned modified monomer unit means a part of the molecular structure of the TFE-based polymer that is derived from the modified monomer.

[0046] The content of each of the above-mentioned polymerization units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

[0047] The above-mentioned modified monomer is not particularly limited as long as it can copolymerize with TFE. For example, perfluoroolefins such as hexafluoropropylene [HFP]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as chlorotrifluoroethylene [CTFE]; perfluorovinyl ether; perfluoroallyl ether; (perfluoroalkyl)ethylene, ethylene, monomers having a polar group, etc. can be mentioned. Further, the modified monomer used may be one type or a plurality of types.

[0048] The above-mentioned perfluorovinyl ether is not particularly limited. For example, the following general formula (A): CF2=CF-ORf 1 (A) (In the formula, Rf 1represents a perfluoro organic group. Examples thereof include perfluoro unsaturated compounds represented by ( ). In the present specification, the above-mentioned "perfluoro organic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen.

[0049] Examples of the above-mentioned perfluorovinyl ether include, for example, in the above general formula (A), Rf 1 is a perfluoro(alkyl vinyl ether) [PAVE] in which the perfluoroalkyl group has 1 to 10 carbon atoms. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

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

[0051] Examples of the above-mentioned perfluorovinyl ether further include, in the above general formula (A), Rf 1 is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 1 is a group represented by the following formula:

[0052]

Chemical formula

[0053] (wherein, m represents an integer of 0 or 1 to 4), and those in which Rf 1 is a group represented by the following formula:

[0054]

Chemical formula

[0055] (wherein, n represents an integer of 1 to 4), and the like.

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

[0057] Examples of the perfluoroallyl ether include, for example, the general formula (B): CF2=CF-CF2-ORf 2 (B) (In the formula, Rf 2 represents a perfluoro organic group.) Fluoromonomers represented by the formula are exemplified.

[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. As the above perfluoroallyl ether, at least one selected from the group consisting of CF2=CF-CF2-O-CF3, CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is preferable, at least one selected from the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is more preferable, and CF2=CF-CF2-O-CF2CF2CF3 is even more preferable.

[0059] The modified monomer is represented by the following general formula (i): CX 1 X 2 =CX 3 X 4 (i) (In the formula, X 1 ~X 3 are each independently H or F. X 4 is F, Cl, Rf or O-Rf. Rf is a perfluoro organic group.) The compound is preferably represented by the formula.

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

[0061] The monomer having the polar group may be a non-fluorine monomer or a fluorine-containing monomer.

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

[0063] The monomer having the above polar group preferably includes a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group (hereinafter referred to as "modified monomer (A)").

[0064] Examples of the hydrophilic group in the above modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, R 7 is H or an organic group, and they 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, -SO3M or -COOM is preferable. R 7 is preferably H or an organic group of C 1-10 and more preferably H or an organic group of C 1-4 and still more preferably H or an alkyl group of C 1-4 . Examples of the above metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferable.

[0065] Examples of the "functional group capable of reacting by radical polymerization" in the above modified monomer (A) include groups having an ethylenically unsaturated bond such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond has the following formula: CX e X g =CX f R- (In the formula, X e , X f and X g are each independently F, Cl, H, CF3, CF2H, CFH2, or CH3; and R is a linking group.). Examples of the linking group of R include the linking group as R a described later. Preferably, -CH=CH2, -CF=CH 2、 -CH=CF 2、Groups having an unsaturated bond such as -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CH=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, -O-CF2-CF=CF2, etc. are exemplified.

[0066] Since the above-mentioned modified monomer (A) has a functional group capable of reacting by radical polymerization, when used in polymerization, it reacts with the fluorine-containing monomer at the initial stage of the polymerization reaction, and it is presumed that particles having a hydrophilic group derived from the above-mentioned modified monomer (A) and high stability are formed. Therefore, when polymerization is carried out in the presence of the above-mentioned modified monomer (A), it is considered that the number of particles increases.

[0067] The above-mentioned modified monomer (A) may be used alone or in combination of two or more.

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

[0069] The modified monomer (A) is preferably at least one selected from the group consisting of compounds represented by the following formulas (4a) to (4e). CF2=CF-(CF2) n1 -Y 3 (4a) (In the formula, n1 represents an integer of 1 to 10, and Y 3 represents -SO3M 1 or -COOM 1 and M 1 represents H, NH4 or an alkali metal.) CF2=CF-(CF2C(CF3)F) n2 -Y 3 (4b) (In the formula, n2 represents an integer of 1 to 5, and Y 3 is the same as the above definition.) CF2=CF-O-(CFX 1 ) n3 -Y 3 (4c) (In the formula, X 1 represents F or CF3, n3 represents an integer from 1 to 10, and Y 3 is the same as defined above.) CF2=CF-O-(CF2CFX 1 O) n4 -CF2CF2-Y 3 (4d) (In the formula, n4 represents an integer from 1 to 10, and Y 3 and X 1 are the same as defined above.) CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (4e) (In the formula, each X 2 is the same, and represents F or H. n5 represents 0 or an integer from 1 to 10, and Y 3 is the same as defined above.) Examples of the alkali metal include Na, K, etc.

[0070] In the above formula (4a), it is preferable that the above n1 is an integer of 5 or less, and more preferably an integer of 2 or less. The above Y 3 is preferably -COOM 1 in terms of obtaining appropriate water solubility and surface activity. M 1 is preferably H or NH4 in that it is difficult to remain as an impurity and the heat resistance of the obtained molded body is improved.

[0071] Examples of the perfluorovinyl alkyl compound represented by the above formula (4a) include, for example, CF2=CFCF2COOM 1 (In the formula, M 1 is the same as defined above.)

[0072] In the above formula (4b), in terms of emulsifying ability, it is preferable that the above n2 is an integer of 3 or less, and Y 3is preferably -COOM in terms of obtaining appropriate water solubility and surface activity. 1 Preferably, 1 M is preferably H or NH4 in terms of being less likely to remain as an impurity and improving the heat resistance of the resulting molded article.

[0073] In the above formula (4c), n3 is preferably an integer of 5 or less in terms of water solubility, and 3 Y is preferably -COOM in terms of obtaining appropriate water solubility and surface activity. 1 Preferably, 1 M is preferably H or NH4 in terms of improving dispersion stability.

[0074] In the above formula (4d), X is preferably -CF3 in terms of surface activity, n4 is preferably an integer of 5 or less in terms of water solubility, and 1 Y is preferably -COOM in terms of obtaining appropriate water solubility and surface activity. 3 Preferably, 1 M is preferably H or NH4. 1

[0075] Examples of the perfluorovinyl ether compound represented by the above formula (4d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM 1 (wherein M 1 represents H, NH4 or an alkali metal).

[0076] In the above formula (4e), n5 is preferably 0 or an integer of 1 to 5 in terms of emulsifying ability, more preferably 0, 1 or 2, and still more preferably 0 or 1. Y 3 is preferably -COOM in terms of obtaining appropriate water solubility and surface activity. 1 Preferably, 1 M is preferably H or NH4 in terms of being less likely to remain as an impurity and improving the heat resistance of the resulting molded article.

[0077] Examples of the perfluorovinyl alkyl compound represented by the above formula (4e) include CH2=CFCF2OCF(CF3)COOM 1 , CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM1 (where M 1 is the same as defined above).)

[0078] As the above-mentioned modified monomer, at least one selected from the group consisting of HFP, PAVE, PFAE, and a monomer having a polar group is preferable in terms of improving stretchability, adhesiveness, and flexibility of the binder sheet. At least one selected from the group consisting of HFP, perfluoro(methyl vinyl ether) [PMVE], perfluoro(propyl vinyl ether) [PPVE], PFBE, a non-fluorine monomer having an acid anhydride residue, and the modified monomer (A) is more preferable. At least one selected from the group consisting of HFP, PMVE, PPVE, a cyclic non-fluorine monomer having an acid anhydride residue, and a compound represented by the general formula (4e) is still more preferable. At least one selected from the group consisting of HFP and PPVE is still more preferable, and HFP is still more preferable.

[0079] The above-mentioned TFE-based polymer may have a core-shell structure. Examples of the TFE-based polymer having a core-shell structure include modified PTFE containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE in the particles. Examples of such modified PTFE include PTFE described in JP-T-2005-527652.

[0080] The above-mentioned TFE-based polymer may be a TFE-based polymer obtained by emulsion polymerization, a TFE-based polymer obtained by suspension polymerization, or a mixture thereof. In terms of obtaining a binder sheet excellent in strength and flexibility, a TFE-based polymer obtained by emulsion polymerization is preferable, and in terms of further improving battery characteristics, a TFE-based polymer obtained using a fluorine-containing surfactant is more preferable.

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

[0082] The TFE-based polymer composition of the present disclosure preferably contains substantially no fluorine-containing compound having a hydrophilic group.

[0083] Examples of the hydrophilic group include -SO3M a , -SO2M a , -OSO2M a , -PO3M a , -COOM a , -OCOM a , and -OM a (wherein M a is -H, a metal atom, -NR 1 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 1 is H or an organic group). At least one selected from the group consisting of these is exemplified. The hydrophilic group may be an ionic group, and is preferably an anionic group.

[0084] Examples of the fluorine-containing compound having a hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 g / mol or less. The molecular weight of the fluorine-containing compound is preferably 800 or less, and more preferably 500 or less. Polymer particles obtained by polymerization carried out in the presence of a fluorine-containing surfactant usually contain, in addition to the TFE-based polymer, the fluorine-containing surfactant. In the present specification, the fluorine-containing surfactant is one used during polymerization. The fluorine-containing compound with a molecular weight of 1000 or less may be a compound that is not added during polymerization, for example, a compound that is by-produced during the polymerization process. In addition, when the fluorine-containing compound with a molecular weight of 1000 or less contains an anionic part and a cationic part, it means a fluorine-containing compound in which the molecular weight of the anionic part is 1000 or less. The fluorine-containing compound with a molecular weight of 1000 or less shall not include TFE-based polymers.

[0085] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include surfactants containing fluorine (anionic fluorine-containing surfactants) in which the molecular weight of the anionic part is 1000 or less. The above-mentioned "anionic part" means the part excluding the cation of the above-mentioned fluorine-containing surfactant. For example, in the case of F(CF2) n1 COOM, it is the part of "F(CF2) n1 COO".

[0086] Examples of the above-mentioned anionic fluorine-containing surfactant include the general formula (N 0 ): X n0 -Rf n0 -Y 0 (N 0 ) (In the formula, X n0 is H, Cl or F. Rf n0 is an alkylene group having 3 to 20 carbon atoms, which is linear, branched or cyclic, and in which part or all of the H is substituted by F, and the alkylene group may contain one or more ether bonds, and part of the H may be substituted by Cl. Y 0 is an anionic group.) Compounds represented by the formula are included.

[0087] Y 0 The anionic group of may be -COOM, -SO2M, or -SO3M, and may be -COOM or -SO3M. M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 7is H or an organic group. Examples of the above metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li. R 7 may be H or an organic group of C 1-10 and may be H or an organic group of C 1-4 and may be H or an organic group of C 1-4 which may be an alkyl group. M may be H, a metal atom, or NR 7 4, and may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 7 4, and may be H, Na, K, Li, or NH4. The above Rf n0 may have 50% or more of H substituted with fluorine.

[0088] Examples of the compound represented by the general formula (N 0 ) include the general formula (N 1 ): X n0 -(CF2) m1 -Y 0 (N 1 ) (wherein X n0 is H, Cl, and F, m1 is an integer of 3 to 15, and Y 0 is as defined above.) The compound represented by the formula, the general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) 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, X n1 is F or CF3, and Y 0 is as defined above.) The compound represented by the formula, the general formula (N 3 ): Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 ) (wherein, Rf n2 is a partially or fully fluorinated alkyl group which may contain an ether bond having 1 to 13 carbon atoms, m3 is an integer of 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y 0 is as defined above.) A compound represented by the general formula (N 4 ): Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 ) (wherein, Rf n4 is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond and / or a chlorine atom having 1 to 12 carbon atoms, Y n1 and Y n2 are the same or different and are H or F, p is 0 or 1, and Y 0 is as defined above.) A compound represented by the general formula (N 5 ):

Chemical formula

[0089] General formula (N 0More specifically, as the compound represented by (), perfluorocarboxylic acid (I) represented by general formula (I), ω-H perfluorocarboxylic acid (II) represented by general formula (II), perfluoroether carboxylic acid (III) represented by general formula (III), perfluoroalkyl alkylene carboxylic acid (IV) represented by general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by general formula (V), perfluoroalkylsulfonic acid (VI) represented by general formula (VI), ω-H perfluorosulfonic acid (VII) represented by general formula (VII), perfluoroalkyl alkylene sulfonic acid (VIII) represented by general formula (VIII), alkyl alkylene carboxylic acid (IX) represented by general formula (IX), fluorocarboxylic acid (X) represented by general formula (X), alkoxyfluorosulfonic acid (XI) represented by general formula (XI), compound (XII) represented by general formula (XII), compound (XIII) represented by the following general formula (XIII), and the like can be mentioned.

[0090] The above perfluorocarboxylic acid (I) is represented by general formula (I): F(CF2) n1 COOM (I) (In the formula, n1 is an integer from 3 to 14, and M is H, a metal atom, NR 7 4, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 7 is H or an organic group.)

[0091] The above ω-H perfluorocarboxylic acid (II) is represented by general formula (II): H(CF2) n2 COOM (II) (In the formula, n2 is an integer from 4 to 15, and M is as defined above.)

[0092] The above perfluoroether carboxylic acid (III) is represented by general formula (III): Rf 1 -O-(CF(CF3)CF2O) n3CF(CF3)COOM (III) (wherein, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.) is represented thereby.

[0093] The above perfluoroalkyl alkylene carboxylic acid (IV) has the general formula (IV): Rf 2 (CH2) n4 Rf 3 COOM (IV) (wherein, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above.) is represented thereby.

[0094] The above alkoxyfluorocarboxylic acid (V) has the general formula (V): Rf 4 -O-CY 1 Y 2 CF2-COOM (V) (wherein, Rf 4 is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond and / or a chlorine atom having 1 to 12 carbon atoms, Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.) is represented thereby.

[0095] The above perfluoroalkylsulfonic acid (VI) has the general formula (VI): F(CF2) n5 SO3M (VI) (wherein, n5 is an integer of 3 to 14, and M is as defined above.) is represented thereby.

[0096] The above ω-H perfluorosulfonic acid (VII) has the general formula (VII): H(CF2) n6SO3M (VII) (In the formula, n6 is an integer from 4 to 14, and M is as defined above.) It is represented by the formula.

[0097] The above perfluoroalkylalkylene sulfonic acid (VIII) has the general formula (VIII): Rf 5 (CH2) n7 SO3M (VIII) (In the formula, Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer from 1 to 3, and M is as defined above.) It is represented by the formula.

[0098] The above alkylalkylene carboxylic acid (IX) has the general formula (IX): Rf 6 (CH2) n8 COOM (IX) (In the formula, Rf 6 is a linear or branched or fully fluorinated alkyl group which may contain an ether bond having 1 to 13 carbon atoms, n8 is an integer from 1 to 3, and M is as defined above.) It is represented by the formula.

[0099] The above fluorocarboxylic acid (X) has the general formula (X): Rf 7 -O-Rf 8 -O-CF2-COOM (X) (In the formula, Rf 7 is a linear or branched or fully fluorinated alkyl group which may contain an ether bond and / or a chlorine atom having 1 to 6 carbon atoms, Rf 8 is a linear or branched or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above.) It is represented by the formula.

[0100] The above alkoxyfluorosulfonic acid (XI) has the general formula (XI): Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI) (wherein, Rf 9 is a linear or branched, optionally chlorine-containing, partially or fully fluorinated alkyl group which may contain an ether bond having 1 to 12 carbon atoms, Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.) is represented thereby.

[0101] The above compound (XII) has the general formula (XII):

Chemical formula

[0102] The above compound (XIII) has the following general formula (XIII): Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM (XIII) (wherein, Rf 11 is a fluoroalkyl group having 1 to 5 carbon atoms which contains chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above.) is represented thereby. Examples of compound (XIII) include CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10CF2COONH4 (a mixture with an average molecular weight of 750, where n9 and n10 are as defined above.) may be mentioned.

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

[0104] The fluorine-containing surfactant may be a single fluorine-containing surfactant or a mixture containing two or more fluorine-containing surfactants.

[0105] Examples of the fluorine-containing surfactant include compounds represented by the following formulas. The fluorine-containing surfactant may be a mixture of these compounds. F(CF2)7COOM, F(CF2)5COOM, H(CF2)6COOM, H(CF2)7COOM, CF3O(CF2)3OCHFCF2COOM, C3F7OCF(CF3)CF2OCF(CF3)COOM, CF3CF2CF2OCF(CF3)COOM, CF3CF2OCF2CF2OCF2COOM, C2F5OCF(CF3)CF2OCF(CF3)COOM, CF3OCF(CF3)CF2OCF(CF3)COOM, CF2ClCF2CF2OCF(CF3)CF2OCF2COOM, CF2ClCF2CF2OCF2CF(CF3)OCF2COOM, CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM, CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, and

Chemical formula

[0106] In the above formulas, M is H, a metal atom or NR 7 4 and may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4 and may be H, Na, K, Li or NH4. R 7 is H or an organic group of C 1-10 and may be H or an organic group of C 1-4 and may be H or an organic group of C 1-4 and may be an alkyl group of.

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

[0108] The amount of the anionic fluorine-containing surfactant is measured by the following method. Weigh 1 g of the sample, add 10 g (12.6 ml) of methanol, perform ultrasonic treatment for 60 minutes to obtain an extract. Appropriately concentrate the obtained extract by nitrogen purging, and measure the fluorine-containing compound in the concentrated extract by LC / MS / MS. Extract the molecular weight information from the obtained LC / MS spectrum and confirm the match with the structural formula of the candidate fluorine-containing compound. Prepare aqueous solutions with a content of 5 levels or more of the standard substance, perform LC / MS analysis on the aqueous solutions of each content, plot the relationship between the content and the area of the area corresponding to that content, and draw a calibration curve. Using the above calibration curve, convert the area of the LC / MS chromatogram of the fluorine-containing compound in the extract into the content of the fluorine-containing compound. Note that the lower limit of quantification in this measurement method is 10 mass ppb.

[0109] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less also include a compound represented by the following general formula (1) (hereinafter also referred to as compound (1)). General formula (1): (H-(CF2) m-1 -COO) p M 1 (In the formula, m is 4 to 20. M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.)

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

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

[0112] The content of the compound (1) is preferably 25 mass ppb or less, more preferably 20 mass ppb or less, still more preferably 15 mass ppb or less, even more preferably 10 mass ppb or less, still more preferably less than 10 mass ppb, even more preferably 1 mass ppb or less, still more preferably less than 1 mass ppb, and particularly preferably less than the lower limit of quantification. The lower limit is not particularly limited and may be an amount less than the lower limit of quantification.

[0113] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight of 1000 or less include a compound represented by the following general formula (2) (hereinafter also referred to as compound (2)). General formula (2): (H-(CF2) n -SO3) q M 2 (In the formula, n is 4 to 20. M 2 is H, a metal atom, NR 5 4 (R 5 is the same as above), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. q is 1 or 2.)

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

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

[0116] The content of compound (2) is preferably 25 mass ppb or less, more preferably 20 mass ppb or less, still more preferably 15 mass ppb or less, even more preferably 10 mass ppb or less, even more preferably less than 10 mass ppb, still 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. The lower limit is not particularly limited and may be an amount less than the lower limit of quantification.

[0117] The contents of compounds (1) and (2) are values measured using liquid chromatography mass spectrometry as described in the examples described later.

[0118] Examples of the fluorine-containing compound having the hydrophilic group include a fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000, that is, a fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000 g / mol.

[0119] Examples of the fluorine-containing compound having a hydrophilic group with a molecular weight exceeding 1000 include, for example, a polymer compound having an ionic group. It should be noted that the above TFE-based polymer is not included in the above polymer compound.

[0120] As the ionic group, an anionic group is preferable. For example, a sulfate group, -COOM a (carboxylate group), a phosphate group, -PO3M a (phosphonate group), -SO3M a (sulfonate group), -SO2M a (sulfinate group), -C(CF3)2OM a (In each formula, M a is -H, a metal atom, -NR 24. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, where R 2 is H or an organic group. Examples include) etc. Among them, -SO3M a -SO2M a -PO3M a and -COOM a At least one selected from the group consisting of is preferred.

[0121] The content of the ionic group is preferably 0.80 meq / g or more, more preferably 1.20 meq / g or more, still more preferably 1.75 meq / g or more, even more preferably 2.00 meq / g or more, and particularly preferably 2.50 meq / g or more with respect to the above polymer compound. The content may also be 10.0 meq / g or less, 8.00 meq / g or less, or 5.00 meq / g or less. The content of the ionic group is determined by calculation from the composition of the above polymer compound.

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

[0123] The above polymer compound preferably has an ion exchange ratio (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the main chain of the above polymer compound relative to the ionic group. A precursor group that becomes ionic upon hydrolysis (for example, -SO2F) is not regarded as an ionic group for the purpose of determining the IXR. The above IXR is preferably 0.5 or more, more preferably 1 or more, still more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. Also, the IXR is preferably 43 or less, more preferably 33 or less, and still more preferably 23 or less. In the above polymer compound, the ionic groups are typically distributed along the polymer main chain. The above polymer compound includes repeating side chains bonded to the polymer main chain, and preferably these side chains have ionic groups.

[0124] The above polymer compound is preferably a water-soluble polymer compound. "Water-soluble" means the property of being easily dissolved or dispersed in an aqueous medium. A water-soluble polymer compound can, for example, not have its particle size measurable by the dynamic light scattering method (DLS), or exhibit a particle size of 5 nm or less. On the other hand, a non-water-soluble polymer compound can, for example, have its particle size measured to be more than 5 nm by the dynamic light scattering method (DLS).

[0125] The number average molecular weight of the above polymer compound is preferably more than 0.1×10 4 , more preferably more than 0.15×10 4 , still more preferably more than 0.2×10 4 , even more preferably more than 0.3×10 4 , still even more preferably more than 0.5×10 4 , still even more preferably more than 1.0×10 4 , particularly preferably more than 2.0×10 4 , especially preferably more than 3.0×10 4 , most preferably more than 75.0×10 4 , preferably 50.0×10 4 or less, more preferably 40.0×10 4 or less, still more preferably 30.0×10 4The following are more preferable, 20.0×10 4 The following are particularly preferable.

[0126] As for the weight average molecular weight of the above polymer compound, 0.1×10 4 is more preferably exceeded, 0.2×10 4 is more preferably exceeded, 0.4×10 4 is still more preferably exceeded, 0.6×10 4 is still more preferably exceeded, 1.0×10 4 is still more preferably exceeded, 2.0×10 4 is particularly preferably exceeded, 5.0×10 4 is most preferably exceeded. Also, 150.0×10 4 is preferably below, 100.0×10 4 is more preferably below, 80.0×10 4 is still more preferably below, 60.0×10 4 is even more preferably below, 40.0×10 4 is particularly preferably below.

[0127] The above number average molecular weight and weight average molecular weight are values calculated by gel permeation chromatography (GPC) using monodisperse polystyrene, or monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) as standards for molecular weight. Also, when measurement by GPC is not possible, the number average molecular weight of the above polymer compound can be determined by 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] It is preferable that the above polymer compound substantially does not contain a fraction with a molecular weight of 1000 or less, more preferably substantially does not contain a fraction with a molecular weight of less than 1500, still more preferably substantially does not contain a fraction with a molecular weight of less than 2000, and particularly preferably substantially does not contain a fraction with a molecular weight of less than 3000. Substantially free of the above fraction means that the content of the fraction in the above polymer compound is 3.0% by mass or less. The content of the fraction is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less, relative to the above polymer compound. The content of the above fraction can be measured by gel permeation chromatography (GPC) or liquid chromatography-mass spectrometry (LC-MS).

[0129] The above polymer compound preferably contains substantially no fluorine-containing compound having a molecular weight of 1000 or less. Substantially free of the above fluorine-containing compound means that the amount of the above fluorine-containing compound is 25 mass ppb or less relative to the above polymer compound. The amount of the above fluorine-containing compound is more preferably less than 25 mass ppb, still more preferably 10 mass ppb or less, still more preferably less than 10 mass ppb, still more preferably 5 mass ppb or less, still more preferably 3 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably less than 1 mass ppb. The lower limit is not particularly limited and may be an amount less than the detection limit. The above fluorine-containing compound having a molecular weight of 1000 or less and its quantification method will be described later.

[0130] The above polymer compound is preferably at least one selected from the group consisting of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the following general formula (I) and a compound (II) represented by the following general formula (II). General formula (I): CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3is independently F, Cl, H or CF3; A 0 is an anionic group; X 2 is H, F, an alkyl group or a fluorinated alkyl group; R is a linking group; Z 1 and Z 2 are independently H, F, an alkyl group or a fluorinated alkyl group; m is an integer of 1 or more.) General formula (II): T X -X A -R FA1 -R FA2 -X A -T X ’ (II) (In the formula, R FA1 is -Rf 1 p -R F -O q -; R FA2 is -Rf 2 p -R FX -O q -; R F is a divalent fluoropolyether group; R FX is a divalent fluoropolyether group containing an anionic group; Rf 1 and Rf 2 are each independently a C 1-6 alkylene group which may be substituted by one or more fluorine atoms; p is each independently 0 or 1; q is each independently 0 or 1; X A are each independently a single bond or a group having a valence of 2 to 10; T X and T X ’ are each independently (i) a C1-C 24 (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and does not have the above anionic group, and (ii) a C1-C containing at least one of the above anionic groups24 It is selected from the group consisting of (hydro)(fluoro)carbon groups.)

[0131] Polymer (I) is a polymer containing polymer units (I) based on monomer (I). Monomer (I) is represented by the following general formula (I). CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, an alkyl group or a fluorinated alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluorinated alkyl group; m is an integer of 1 or more.) X 2 is preferably F, Cl, H or CF3. Also, Z 1 and Z 2 are preferably F or CF3.)

[0132] In the present disclosure, the anionic group includes, in addition to anionic groups such as a sulfate group and a carboxylate group, functional groups that give anionic groups such as an acid group like -COOH and an acid salt group like -COONH4. Preferred anionic groups include a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group, a sulfinate group, or -C(CF3)2OM a (In the formula, M a is -H, a metal atom, -NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group.)

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

[0134] R is a linking group. In the present disclosure, the "linking group" is a (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. The number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. The upper limit is not limited, but for example, it may be 100 or less, or 50 or less.

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

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

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

[0138] The polymer (I) is also preferably highly fluorinated. For example, anionic groups (A a ) such as phosphate group moieties (e.g., CH2OP(O)(OM a )2) and sulfate group moieties (e.g., CH2OS(O)2OM 0It is preferable 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, except for

[0139] The monomer (I) and the polymer (I) preferably have C-F bonds and no C-H bonds, except for the anionic group (A 0 ). That is, in the general formula (I), X 1 , X 2 , and X 3 are all F, and R is preferably a perfluoroalkylene group having 1 or more carbon atoms. The perfluoroalkylene group may be linear or branched, 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) preferably have at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom, except for the anionic group (A 0 ).

[0141] The anionic group (A 0 ) is -SO3M a , -OSO3M a , -SO2M a , -COOM a , -SO2NR’CH2COOM a , -CH2OP(O)(OM a )2, [-CH2O]2P(O)(OM a ), -CH2CH2OP(O)(OM a )2, [-CH2CH2O]2P(O)(OM a ), -CH2CH2OSO3M a , -P(O)(OM a )2, -SO2NR’CH2CH2OP(O)(OM a )2, [-SO2NR’CH2CH2O]2P(O)(OM a)、 -CH2OSO3M a 、 -SO2NR’CH2CH2OSO3M a 、 or, -C(CF3)2OM a may be. Among them, -SO3M a 、 -OSO3M a 、 -COOM a 、 -P(O)(OM a )2 or C(CF3)2OM a is preferred, -COOM a 、 -SO3M a 、 -OSO3M a or C(CF3)2OM a is more preferred, -SO3M a 、 -COOM a or P(O)(OM a )2 is even more preferred, -SO3M a or COOM a is particularly preferred, -COOM a is most preferred.

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

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

[0144] M a is preferably -H, a metal atom or NR 2 4, more preferably -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 2 4, even more preferably -H, -Na, -K, -Li or NH4, even more preferably -H, -Na, -K or NH4, particularly preferably -H, -Na or NH4, and most preferably -H or NH4.

[0145] In the polymer (I), each polymerization unit (I) may have different anionic groups or 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 polymerization unit (Ia) based on the monomer represented by the general formula (Ia). CF2=CF-O-Rf 0 -A 0 (Ia) (In the formula, A 0 is an anionic group, and Rf 0 is perfluorinated and may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and optionally additionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen. It is a perfluorinated divalent linking group.)

[0147] The monomer (I) is preferably a monomer represented by the general formula (Ib). The polymer (I) is preferably a polymer containing a polymerization unit (Ib) based on the monomer represented by the general formula (Ib). CH2=CH-O-Rf 0 -A 0 (Ib) (In the formula, A 0 is an anionic group, and Rf 0 is the perfluorinated divalent linking group defined in formula Ia.)

[0148] In the general formula (I), A 0 is preferably one preferred form which is a sulfate group. A 0 is, for example, -CH2OSO3M a , -CH2CH2OSO3M a , or -SO2NR’CH2CH2OSO3M a , where R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0149] A 0When it is a sulfate group, examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2CH2OSO3M a ), CH2=CH(O(CF2)4CH2OSO3M a ), CF2=CF(O(CF2)4CH2OSO3M a ), CF2=CF(OCF2CF(CF3)CH2OSO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M a ), CH2=CH(O(CF2)4CH2OSO3M a ), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M a ), CH2=CH(OCF2CF2CH2OSO3M a ), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M a ), CH2=CH(OCF2CF2CF2CH2OSO3M a ), etc. In the above formula, M a is the same as above.

[0150] In the general formula (I), it is also a preferred form that A 0 is a sulfonate group. Examples of A 0 include -SO3M a . In the formula, M a is the same as above.

[0151] When A 0 is a sulfonate group, examples of the monomer represented by the general formula (I) include CF2=CF(OCF2CF2SO3M a ), CF2=CF(O(CF2)3SO3M a ), CF2=CF(O(CF2)4SO3M a ), CF2=CF(OCF2CF(CF3)SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M a ), CH2=CH(OCF2CF2SO3M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M a)、CH2=CH(O(CF2)4SO3M a )、CH2=CH(O(CF2)3SO3M a ) etc. are mentioned. In the above formula, M a is the same as above.

[0152] In general formula (I), A 0 being a sulfinate group is also one of the preferred forms. As A 0 , for example, it is -SO2M a , and in the formula, M a is the same as above.

[0153] A 0 When A is a sulfinate group, as the monomer represented by general formula (I), there are CF2=CF(OCF2CF2SO2M a ), CF2=CF(O(CF2)3SO2M a ), CF2=CF(O(CF2)4SO2M a ), CF2=CF(OCF2CF(CF3)SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2SO2M a ), CH2=CH(OCF2CF2SO2M a ), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2M a ), CH2=CH(O(CF2)4SO2M a ), CH2=CH(O(CF2)3SO2M a ) etc. are mentioned. In the above formula, M a is the same as above.

[0154] In general formula (I), A 0 being a carboxylate group is also one of the preferred forms. As A 0 , for example, it is COOM a or SO2NR’CH2COOM a , and in the formula, R’ is H or an alkyl group with 1 to 4 carbon atoms, and M a is the same as above. When A 0 is a carboxylate group, as the monomer represented by general formula (I), there is CF2=CF(OCF2CF2COOMa )、CF2=CF(O(CF2)3COOM a )、CF2=CF(O(CF2)4COOM a )、CF2=CF(O(CF2)5COOM a )、CF2=CF(OCF2CF(CF3)COOM a )、CF2=CF(OCF2CF(CF3)O(CF2) n COOM a )(n is greater than 1), CH2=CH(OCF2CF2COOM a )、CH2=CH(O(CF2)4COOM a )、CH2=CH(O(CF2)3COOM a )、CF2=CF(OCF2CF2SO2NR’CH2COOM a )、CF2=CF(O(CF2)4SO2NR’CH2COOM a )、CF2=CF(OCF2CF(CF3)SO2NR’CH2COOM a )、CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM a )、CH2=CH(OCF2CF2SO2NR’CH2COOM a )、CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM a )、CH2=CH(O(CF2)4SO2NR’CH2COOM a )、CH2=CH(O(CF2)3SO2NR’CH2COOM a ) etc. may be mentioned. In the above formula, R’ is H or an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0155] In general formula (I), it is also a preferred form that A 0 is a phosphate group. Examples of A 0 include, for example, -CH2OP(O)(OM a )2, [-CH2O]2P(O)(OM a )、-CH2CH2OP(O)(OM a )2、[-CH2CH2O]2P(O)(OM a )、[-SO2NR’CH2CH2O]2P(O)(OMa ) or SO2NR’CH2CH2OP(O)(OM a )2, wherein R’ is an alkyl group having 1 to 4 carbon atoms, and M a is the same as above.

[0156] A 0 is phosphate, and the monomer represented by the general formula (I) includes CF2=CF(OCF2CF2CH2OP(O)(OM a )2), CF2=CF(O(CF2)4CH2OP(O)(OM a )2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM a )2), CH2=CH(OCF2CF2CH2OP(O)(OM a )2), CH2=CH(O(CF2)4CH2OP(O)(OM a )2), CH2=CH(O(CF2)3CH2OP(O)(OM a )2), etc. In the above formulas, M a is the same as above.

[0157] In the general formula (I), it is also a preferred form that A 0 is a phosphonate group. When A 0 is a phosphonate group, the monomer represented by the general formula (I) includes CF2=CF(OCF2CF2P(O)(OM a )2), CF2=CF(O(CF2)4P(O)(OM a )2), CF2=CF(OCF2CF(CF3)P(O)(OM a )2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM a )2), CH2=CH(OCF2CF2P(O)(OM a)2), CH2=CH(O(CF2)4P(O)(OM a )2), CH2=CH(O(CF2)3P(O)(OM a )2) may be mentioned, where M a is the same as above.

[0158] The monomer (I) is preferably the monomer (1) represented by the general formula (1). The polymer (I) is preferably the polymer (1) containing the polymerization unit (1) based on the monomer represented by the general formula (1). CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X is the same or different and is -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, and Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms. A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a is -H, a metal atom, -NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group.) However, at least one of X, Y and Z contains a fluorine atom.)

[0159] In the production method of the present disclosure, the monomer (1) represented by the general formula (1) and other monomers may be copolymerized. The polymer (1) may be a homopolymer of the monomer (1) represented by the general formula (1), or a copolymer with other monomers.

[0160] The above-mentioned fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms does not include a structure in which an oxygen atom is at the end, and is an alkylene group containing an ether bond between carbon atoms.

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

[0162] In general formula (1), Y is -H, -F, an alkyl group, or a fluorinated alkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above fluorinated alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above Y, -H, -F or CF3 is preferable, and -F is more preferable.

[0163] In general formula (1), Z's are the same or different and are -H, -F, an alkyl group, or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above fluorinated alkyl group is an alkyl group that contains at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms of the above fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above Z, -H, -F or CF3 is preferable, and -F is more preferable.

[0164] In general formula (1), at least one of the above X, Y and Z contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

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

[0166] The number of carbon atoms in the above fluorine-containing alkylene group is preferably 2 or more. Further, the number of carbon atoms in the above fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. Examples of the above fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CF2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, and the like. The above fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0167] The number of carbon atoms in the fluorine-containing alkylene group having the above ether bond is preferably 3 or more. Further, the number of carbon atoms in the fluorine-containing alkylene group having the above ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorine-containing alkylene group having the above ether bond is, for example, represented by the general formula:

Chemical formula

[0168] Specific examples of the fluorine-containing alkylene group having the above ether bond include -CF2CF(CF3)OCF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n-CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. are exemplified. The fluorine-containing alkylene group having the above ether bond is preferably a perfluoroalkylene group.)

[0169] In the general formula (1), A is -COOM a , -SO3M a , -OSO3M a , -SO2M a , or C(CF3)2OM a (M a is H, a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group).

[0170] R 2 is preferably H or an organic group of C 1-10 , more preferably H or an organic group of C 1-4 , and even more preferably H or an alkyl group of C 1-4 .

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

[0172] M a is preferably H, a metal atom or NR 2 4, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 2 4, even more preferably H, Na, K, Li or NH4, even more preferably H, Na, K or NH4, particularly preferably H, Na or NH4, and most preferably H or NH4.

[0173] A is -COOM a or SO3M a is preferred, and -COOM a is more preferred.

[0174] Examples of the monomer represented by the general formula (1) include, for example, the general formula (1a): CX2 = CFCF2 - O - (CF(CF3)CF2O) n5 -CF(CF3)-A (1a) (In the formula, each X is the same and represents F or H. n5 represents 0 or an integer from 1 to 10, and A is the same as defined above.) Monomers represented by this formula are exemplified.

[0175] In the 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 terms of being able to obtain particles with a small primary particle diameter.

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

[0177] The monomer (1) is preferably a monomer represented by the general formula (1A). The polymerization unit (1) is preferably a polymerization unit (1A) based on the monomer represented by the general formula (1A). CH2 = CF(-CF2 - O - Rf - A) (1A) (In the formula, Rf and A are the same as above.)

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

[0179] Specific examples of the monomer represented by the formula (1A) include the general formula [Chemical formula] (In the formula, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; p1 + q1 + r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, provided that when Z 3 and Z 4 are both H, p1 + q1 + r1 + s1 is not 0; A is the same as defined above). Examples of the monomer represented by the formula include. More specifically, [Chemical formula] etc. are preferably mentioned, and among them [Chemical formula] is preferably the case.

[0180] As the monomer represented by the general formula (1A), it is preferable that A in the formula (1A) is -COOM a , and in particular, CH2 = CFCF2OCF(CF3)COOM a , and CH2 = CFCF2OCF(CF3)CF2OCF(CF3)COOM a (In the formula, M a is the same as defined above.) At least one selected from the group consisting of is preferable, and CH2 = CFCF2OCF(CF3)COOM a is more preferable.

[0181] Also, examples of the monomer represented by the general formula (1) include monomers represented by the following formula. CF2 = CFCF2 - O - Rf - A (In the formula, Rf and A are the same as above)

[0182] More specifically, [Chemical formula] etc. are included.

[0183] The monomer (I) is preferably the monomer (2) represented by the general formula (2). The polymer (I) is preferably the polymer (2) containing the polymerization unit (2) based on the monomer represented by the general formula (2). CX2=CY(-O-Rf-A) (2) (In the formula, X is the same or different and is -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond or a keto group and having 2 to 100 carbon atoms. A is the same as described above.)

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

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

[0186] In the general formula (2), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom and may have 1 or more carbon atoms. The carbon number of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom and may have 1 or more carbon atoms. The carbon number of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As Y, -H, -F or CF3 is preferable, and -F is more preferable.

[0187] In the general formula (2), at least one of X and Y preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

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

[0189] The number of carbon atoms of the fluorine-containing alkylene group of Rf is preferably 2 or more. Further, it is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, -CF2CF2CF2-, CF2CF2CF2CF2-, etc. The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0190] The number of carbon atoms of the fluorine-containing alkylene group having the above ether bond is preferably 3 or more. Further, the number of carbon atoms of the fluorine-containing alkylene group having the above ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less, and particularly preferably 5 or less. The fluorine-containing alkylene group having the above ether bond is, for example, represented by the general formula:

Chemical formula

[0191] Specific examples of the fluorine-containing alkylene group having the ether bond include -CF2CF(CF3)OCF2CF2-, -CF2CF(CF3)OCF2CF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n -CF(CF3)CH2-(wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having the ether bond is preferably a perfluoroalkylene group.

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

[0193] Specific examples of the fluorine-containing alkylene group having the keto group include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2CF2-, etc. The fluorine-containing alkylene group having the 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 with water added to the keto group include -CF2CF(CF3)C(OH)2-CF2-, -CF2CF(CF3)C(OH)2-CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2CF2-, and the like.

[0195] The monomer represented by the general formula (2) is preferably at least one selected from the group consisting of the monomers represented by the general formulas (2a), (2b), (2c), (2d), (2e), (2f), and (2g). CF2=CF-O-(CF2) n1 -A (2a) (In the formula, n1 represents an integer from 1 to 10, and A is the same as defined above.) CF2=CF-O-(CF2C(CF3)F) n2 -A (2b) (In the formula, n2 represents an integer from 1 to 5, and A has the same definition as above.) CF2=CF-O-(CFX 1 ) n3 -A (2c) (In the formula, X 1 represents F or CF3, n3 represents an integer from 1 to 10, and A has the same definition as above.) CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -A (2d) (In the formula, n4 represents an integer from 1 to 10, n6 represents an integer from 1 to 3, and A and X 1 have the same definitions as above.) CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-A (2e) (In the formula, n5 represents an integer from 0 to 10, and A and X 1 have the same definitions as above.) CF2=CF-O-(CF2) n7 -O-(CF2) n8 -A (2f) (In the formula, n7 represents an integer from 1 to 10, and n8 represents an integer from 1 to 3. A is the same as the above definition.) CF2=CF[OCF2CF(CF3)] n9 O(CF2) n10 O[CF(CF3)CF2O] n11 CF(CF3)-A (2g) (In the formula, n9 represents an integer from 0 to 5, n10 represents an integer from 1 to 8, and n11 represents an integer from 0 to 5. A is the same as the above definition.)

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

[0197] Examples of the monomer represented by general formula (2a) include CF2=CF-O-CF2COOM a , CF2=CF(OCF2CF2COOM a ), CF2=CF(O(CF2)3COOM a ), CF2=CF(OCF2CF2SO3M a ), CF2=CFOCF2SO3M a , CF2=CFOCF2CF2CF2SO3M a (In the formula, M a is the same as the above definition.)

[0198] In general formula (2b), it is preferable that n2 is an integer of 3 or less in terms of the dispersion stability of the resulting composition.

[0199] In general formula (2c), it is preferable that n3 is an integer of 5 or less in terms of water solubility, the above A is preferably -COOM a , and the above M a is preferably H, Na, or NH4.

[0200] In general formula (2d), X 1 is preferably -CF3 in terms of the dispersion stability of the composition, n4 is preferably an integer of 5 or less in terms of water solubility, and A is -COOM ais preferably M a is preferably H, Na or NH4.

[0201] Examples of the monomer represented by the general formula (2d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM a , CF2=CFOCF2CF(CF3)OCF2COOM a , CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM a , CF2=CFOCF2CF(CF3)OCF2SO3M a , CF2=CFOCF2CF(CF3)OCF2CF2SO3M a , CF2=CFOCF2CF(CF3)OCF2CF2CF2SO3M a (wherein M a represents H, NH4 or an alkali metal.)

[0202] In the general formula (2e), n5 is preferably an integer of 5 or less in terms of water solubility, and A is -COOM a is preferably, and M a is preferably H or NH4.

[0203] Examples of the monomer represented by the general formula (2e) include CF2=CFOCF2CF2CF2COOM a (wherein M a represents H, Na, NH4 or an alkali metal.)

[0204] In the general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, and A is -COOM a or SO3M a is preferably, and -COOM a is more preferable. M a is preferably H, Na, K or NH4.

[0205] Examples of the monomer represented by the general formula (2f) include CF2=CF-O-(CF2)3-O-CF2-COOM a (wherein Ma represents H, NH4 or an alkali metal. ) can be mentioned.

[0206] In general formula (2g), n9 is preferably an integer of 3 or less in terms of water solubility, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, and A is -COOM a or SO3M a is preferable, and -COOM a is more preferable. M a is preferably H, Na, K or NH4.

[0207] Examples of the monomer represented by general formula (2g) include CF2=CFO(CF2)2OCF(CF3)COOM a , CF2=CFOCF2CF2OCF(CF3)CF2OCF(CF3)COOM a , CF2=CFOCF2CF(CF3)OCF2CF2OCF(CF3)COOM a , CF2=CF[OCF2CF(CF3)]2O(CF2)2O[CF(CF3)CF2O]CF(CF3)COOM a , CF2=CF[OCF2CF(CF3)]3O(CF2)2O[CF(CF3)CF2O]3CF(CF3)COOM a (wherein, M a represents H, NH4 or an alkali metal. ) can be mentioned.

[0208] The monomer (I) is also preferably the monomer (3) represented by general formula (3). The polymer (I) is also preferably a polymer (3) containing a polymerization unit (3) based on the monomer represented by general formula (3). CX2=CY(-Rf-A) (3) (wherein, X is the same or different and is -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms. A is the same as above. )

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

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

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

[0212] The monomer represented by the general formula (3) is the general formula (3a): CF2=CF-(CF2) n1 -A (3a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) The monomer represented by the formula, and the general formula (3b): CF2=CF-(CF2C(CF3)F) n2 -A (3b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as defined above.) At least one selected from the group consisting of monomers represented by the formula is preferred.

[0213] In the general formula (3a) and the general formula (3b), A is -SO3M a Or COOM a Is preferred, and M a Is H, a metal atom, NR 2 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent. R 2 Represents H or an organic group.

[0214] In the general formula (3a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. A is -COOMa is preferably M a is preferably H or NH4.

[0215] Examples of the monomer represented by the general formula (3a) include CF2 = CFCF2COOM a (wherein M a is the same as defined above).

[0216] In the general formula (3b), n2 is preferably an integer of 3 or less in terms of the dispersion stability of the resulting composition, and A is preferably -COOM a is preferably M a is preferably H or NH4.

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

[0218] The monomer (I) is also preferably at least one selected from the group consisting of monomers represented by the general formula (4a) and the general formula (4b). The polymer (I) is also preferably a polymer (4) containing a polymerization unit (4) based on at least one monomer selected from the group consisting of monomers represented by the general formula (4a) and the general formula (4b). CF2 = CF - CF2 - O - Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4a) (wherein Z 1 , Z 2 and A are the same as defined above, Q F1 and Q F2 are the same or different and are a single bond, a fluorine-containing alkylene group which may contain an ether bond between carbon atoms, or a fluorine-containing oxyalkylene group which may contain an ether bond between carbon atoms) CF2 = CF - O - Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4b) (wherein Z1 , Z 2 , A, Q F1 and Q F2 is the same as the above definition)

[0219] Examples of the monomers represented by general formula (4a) and general formula (4b) include

Chemical formula

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

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

[0222] As the other monomer, a monomer represented by the general formula CFR=CR2 (wherein R is independently H, F or a perfluoroalkyl group having 1 to 4 carbon atoms) is preferable. Further, as the other monomer, a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms is preferable. Examples of the other monomer include CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E form), CHF=CHCF3 (Z form), and the like. Among them, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2) is preferable in terms of good copolymerizability, and at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride is more preferable. Therefore, the polymerization unit based on the other monomer is preferably a polymerization unit based on tetrafluoroethylene. The polymerization units based on the other monomer may be the same or different in each occurrence, and the polymer (I) may contain polymerization units based on two or more different other monomers.

[0223] Examples of the other monomer also include the general formula (n1-2):

Chemical formula

[0224] Specific examples include CH2=CFCF2-O-Rf 3 , CF2=CF-O-Rf 3 , CF2=CFCF2-O-Rf 3 , CF2=CF-Rf 3 , CH2=CH-Rf 3 , CH2=CH-O-Rf 3 (In the formula, Rf 3 is the same as the above formula (n1-2)) and the like are preferably mentioned.

[0225] Examples of the other monomer also include the formula (n2-1):

Chemical formula

Chemical formula

[0226] As the other monomer, the formula (n2-2): CH2=CHO-Rf 5 (n2-2) (wherein, Rf 5 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond and having 2 to 100 carbon atoms). Examples thereof also include fluorine-containing vinyl ethers.

[0227] Specific examples of the monomer of the general formula (n2-2) include

Chemical formula

[0228] More specifically,

Chemical formula

[0229] In addition, the general formula (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (wherein, Rf 6 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond and having 2 to 100 carbon atoms). Examples thereof also include fluorine-containing allyl ethers, the general formula (n2-4): CH2=CH-Rf 7 (n2-4) (wherein, Rf7 Examples also include fluorine-containing vinyl monomers represented by a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond with 2 to 100 carbon atoms).

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

Chemical formula

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

[0232] In the polymer (I), the content of the polymerization unit (I) is, in descending 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, 90 mol% or more, based on all the polymerization units. It is particularly preferable that the content of the polymerization unit (I) is substantially 100 mol%, and it is most preferable that the polymer (I) consists only of the polymerization unit (I).

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

[0234] The number average molecular weight of the polymer (I) is preferably 0.1×10 4 or more, more preferably 0.2×10 4 or more, still more preferably 0.3×10 4 or more, even more preferably 0.4×10 4 or more, particularly more preferably 0.5×10 4 or more, especially preferably 1.0×10 4 or more, particularly preferably 3.0×10 4 or more, especially particularly preferably 3.1×10 4 or more, most preferably. Further, it is preferably 75.0×10 4 or less, more preferably 50.0×10 4 or less, still more preferably 40.0×10 4 or less, particularly more preferably 30.0×10 4 or less, especially particularly preferably 20.0×10 4 or less, particularly preferably. The number average molecular weight and the weight average molecular weight are values calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. Further, when measurement by GPC cannot be performed, the number average molecular weight of the 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] As the lower limit of the weight average molecular weight of the polymer (I), preferably, in descending order, 0.2×104 Above, 0.4×10 4 Above, 0.6×10 4 Above, 0.8×10 4 Above, 1.0×10 4 Above, 2.0×10 4 Above, 5.0×10 4 Above, 10.0×10 4 Above, 15.0×10 4 Above, 20.0×10 4 Above, 25.0×10 4 It is as above. Further, as the upper limit of the weight average molecular weight of the polymer (I), in descending order of preference, 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 It is below.

[0236] The polymer (I) preferably has an ion exchange rate (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the polymer main chain with respect to the ionic group. A precursor group that becomes ionic by hydrolysis (for example, -SO2F) is not regarded as an ionic group for the purpose of determining the IXR.

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

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

[0239] In the polymer (I), the ionic group (anionic group) is typically distributed along the polymer main chain. The polymer (I) includes a polymer main chain together with repeating side chains bonded to this main chain, and it is preferable that these side chains have ionic groups.

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

[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 a salt is used, preferably, the salt is an alkali metal salt or an ammonium salt. A preferred ionic group is a sulfonate group.

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

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

[0244] The viscosity of the aqueous solution of the polymer (I) can be specified by adjusting the content of the polymer (I) in the aqueous solution to 33% by mass with respect to the aqueous solution and measuring the viscosity of the obtained aqueous solution at 20 °C using a tuning fork vibration type viscometer (model number: SV-10) manufactured by A&D Company Limited.

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

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

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

[0248] The acid value of polymer (I) is, when polymer (I) has an anionic group other than an acidic functional group, for example, -COOM a , -SO3M a , -OSO3M a or C(CF3)2OM a (M a is a metal atom, NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 2 is H or an organic group), measurable by acid-base titration after converting these groups to acidic groups.

[0249] Compound (II) is represented by general formula (II). General formula (II): T X -X A -R FA1 -R FA2 -X A -T X ’ (II) (In the formula, R FA1 is -Rf1 p -R F -O q - and R FA2 is -Rf 2 p -R FX -O q - and R F is a divalent fluoropolyether group R FX is a divalent fluoropolyether group containing an anionic group Rf 1 and Rf 2 are each independently a C alkylene group which may be substituted by one or more fluorine atoms 1-6 - p is each independently 0 or 1 q is each independently 0 or 1 X A are each independently a single bond or a group having a valence of 2 to 10 T X and T X ’ are each independently (i) a C1-C (hydro)(fluoro)carbon group which may contain one or more of H, O and Cl and does not have the above anionic group, and (ii) a C1-C (hydro)(fluoro)carbon group containing at least one of the above anionic groups. 24 (Selected from the group consisting of) 24 (Selected from the group consisting of)

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

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

[0252] In formula (II), Rf 1and Rf 2 is each independently a C alkylene group which may be substituted by one or more fluorine atoms. 1-6

[0253] The "C alkylene group" in the above-mentioned C alkylene group which may be substituted by one or more fluorine atoms 1-6 may be linear or branched, preferably is a linear or branched C alkylene group, 1-6 more preferably is a linear C alkylene group. 1-3 1-3

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

[0255] The above-mentioned C perfluoroalkylene group 1-6 may be linear or branched, preferably is a linear or branched C perfluoroalkylene group, 1-3 more preferably is a linear C perfluoroalkylene group, 1-3 specifically is -CF2-, -CF2CF2-, or -CF2CF2CF2-.

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

[0257] In the above formula, q is each 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 a group of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [wherein: R Fa is each independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.] and is a group represented by

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

[0261] a, b, c, d, e and f may each independently be preferably an integer of 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, still more preferably 20 or more, and may be, for example, 25 or more or 30 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0263] These repeating units may be linear, branched, or may contain a ring structure. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0264] The above ring structure can be a three-membered ring, four-membered ring, five-membered ring, or six-membered ring as follows. [Chemical formula] [In the formula, * indicates the bonding position.]

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

[0266] The repeating unit having a ring structure may preferably be the following unit.

Chemical formula

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

[0268] In one aspect, the repeating unit is branched.

[0269] In one aspect, R F is a group represented by any of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer from 1 to 200, e is 0 or 1, preferably 0.], -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200, the sum of c, d, e and f is 2 or more, the order of existence of each repeating unit enclosed in parentheses with c, d, e or f attached is arbitrary in the formula.], -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups, g is an integer from 2 to 100.], -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, R 6’ is OCF2 or OC2F4, R 7’ is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g’ is an integer from 2 to 100, R r is [Chemical formula] (In the formula, * indicates the bonding position.) is as follows; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently integers from 0 to 200, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f attached is arbitrary in the formula.] -(OC6F 12 )a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [wherein, f is an integer of 1 or more and 200 or less, and a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula.]

[0270] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. OC3F6 in the above formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). In one embodiment, e is 0. In another embodiment, e is 1. (OC2F4) in the above formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2).

[0271] In the above formula (f2), e and f are each independently preferably an integer of 5 to 200, more preferably 10 to 200. Also, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f - represented by the group. In another embodiment, the formula (f2) may be a group represented by -(OC2F4) e -(OCF2) f - represented by the group.

[0272] In the above formula (f3), R 6is preferably OC2F4. In the above (f3), R 7 is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably OC3F6 or OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, but for example, -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4- etc. may be mentioned. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either linear or branched, preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g -.

[0273] In the above formula (f4), R 6 , R 7 and g have the same meanings as described in the above formula (f3) and have the same embodiments. R 6’ , R 7’ and g' each have the same meanings as R 6 , R 7 and g described in the above formula (f3) and have the same embodiments. R r is preferably

Chemical formula

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

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

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

[0283] R F In R, 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, still more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85. By setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The greater the e / f ratio, the more the stability of the compound can be improved.

[0284] In one aspect, from the viewpoint of heat resistance, the e / f ratio may preferably be 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 above anionic group includes, in addition to anionic groups such as sulfate groups and carboxylate groups, functional groups that give anionic groups such as acid groups like -COOH and acid salt groups like -COONH4. Examples of the anionic group include sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, or -C(CF3)2OM a (wherein M a is -H, a metal atom, -NR 2 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 2 is H or an organic group.) is preferred.

[0286] R FX The above fluoropolyether group in R may be a group in which one or more hydrogen atoms of the polyether group are substituted with fluorine atoms, and is preferably a perfluoropolyether group.

[0287] R FX has, as a repeating unit, (a1)-CF2CF(G x )O- (b1)-CF(G x )O- (c1)-CF2(CF2) x1 CF(G x )(CF2) x2 O-(where X1 and X2 are zero or integers from 1 to 2, provided that X1 + X2 is at least 1), [wherein G x is a C1-C5 perfluoro(oxy)alkylene group containing at least one anionic group as detailed above] and is preferably a divalent fluoropolyether group having units selected from the group consisting of

[0288] Note that the order of existence of the repeating units constituting R F and R FX is arbitrary.

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

[0290] In formula (II), X A is understood to be a linker that connects the fluoropolyether moiety (R FA1 and R FA2 ) and the moiety containing an anionic group (T X and T X '). Therefore, the X A may be a single bond or any group as long as the compound represented by formula (II) can exist stably.

[0291] X Aare 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] The above X A The divalent to decavalent group in is preferably a divalent to octavalent group. In one embodiment, such divalent to decavalent group is preferably a divalent to tetravalent group, more preferably a divalent group. In another embodiment, such 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 above divalent group is preferably an oxygen atom, a sulfur atom, NH, CO, or a divalent organic group, more preferably an oxygen atom or a divalent organic group, still more preferably a divalent organic group.

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

[0302] In a preferred embodiment, the above X A are each independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -. R 52 represents a single bond, -(CH2) t5 -, or an o-, m-, or p-phenylene group, preferably -(CH2) t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Here, R 52 (typically the hydrogen atom of R 52 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred embodiment, R 52 is not substituted with these groups.

[0303] Preferably, the above X A are each independently a single bond, a C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 5 - [wherein, R 51 and R 52 are as defined above, and X 53 is -O- -S- -C(O)O- -CONR 54 - -O-CONR 54 - -Si(R 53 )2- -(Si(R 53 )2O) m5 -Si(R 53 )2- -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2- -O-(CH2) u5 -Si(R 53 )2-O-Si(R 53 )2-CH2CH2-Si(R 53 )2-O-Si(R 53 )2- -O-(CH2) u5 -Si(OCH3)2OSi(OCH3)2- -CONR 54 -(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2- -CONR 54 -(CH2) u5 -N(R 54 )- or -CONR 54 -(o-, m- or p-phenylene)-Si(R 53 )2- (wherein, R 53 , R 54 and m5 are as defined above, and u5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3.) represents, X 54 is, -S-, -C(O)O-, -CONR 54 -, -O-CONR 54 -, -CONR 54 -(CH2) u5 -(Si(R 54 )2O) m5 -Si(R 54 )2-, -CONR 54 -(CH2) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 )2- (wherein each symbol has the same meaning as above.) represents.] can be.

[0304] More preferably, the above X A are each independently a single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -, -(CH2) s5 -X 53 -(CH2) t5 -, -X 54 -, or -X 54 -(CH2) t5 -, [wherein X 53 , X 54 , s5 and t5 have the same meaning as above.] is.

[0305] More preferably, the above X A are each independently a single bond, C 1-20 an alkylene group, -(CH2) s5 -X 53 -(CH2) t5 -, or -X 54 -(CH2) t5 - [wherein each symbol has the same meaning as defined above.] may be.

[0306] In a preferred embodiment, the above X A are each independently a single bond C 1-20 an alkylene group, -(CH2) s5 -X 53 -, or -(CH2) s5 -X 53 -(CH2) t5 - [wherein X 53 is -O-, -CONR 54 -, or -O-CONR 54 -, and R 54 are each independently a hydrogen atom, a phenyl group or a C 1-6 alkyl group, and s5 is an integer from 1 to 20, t5 is an integer from 1 to 20.] may be.

[0307] In a preferred embodiment, the above X A are each independently -(CH2) s5 -O-(CH2) t5 - -CONR 54 -(CH2) t5 - [wherein R 54 are each independently a hydrogen atom, a phenyl group or a C 1-6 alkyl group, and s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It can be.

[0308] In one aspect, the above X A are each independently a single bond, C 1-20 an alkylene group, -(CH2) s5 -O-(CH2) t5 -, -(CH2) s5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, -(CH2) s5 -O-(CH2) u5 -(Si(R 53 )2O) m5 -Si(R 53 )2-(CH2) t5 -, or -(CH2) s5 -O-(CH2) t5 -Si(R 53 )2-(CH2) u5 -Si(R 53 )2-(C v H 2v )- [wherein, R 53 , m5, s5, t5 and u5 have the same meanings as above, v is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. It is.

[0309] In the above formula, -(C v H 2v )- may be linear or branched, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0310] The above X A are each independently a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably, C1-3 It may be substituted by one or more substituents selected from (perfluoroalkyl group). In one embodiment, X A is unsubstituted.

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

[0312] In another embodiment, examples of X A include the following groups:

Chemical formula

Chemical formula

Chemical formula

[0313] Specific examples of the above X A are, for example: a single bond, -CH2OCH2-, -CH2O(CH2)2-, -CH2O(CH2)3-, -CH2O(CH2)4-, -CH2O(CH2)5-, -CH2O(CH2)6-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-, -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -CH2OCF2CHFOCF2-, -CH2OCF2CHFOCF2CF2-, -CH2OCF2CHFOCF2CF2CF2-, -CH2OCH2CF2CF2OCF2-, -CH2OCH2CF2CF2OCF2CF2-, -CH2OCH2CF2CF2OCF2CF2CF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-, -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF2-、 -CH2OCH2CHFCF2OCF2CF2-、 -CH2OCH2CHFCF2OCF2CF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、 -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、 -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、 -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、 -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、 -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、 -(CH2)2-Si(CH3)2-(CH2)2-、 -CH2-、 -(CH2)2-、 -(CH2)3-、 -(CH2)4-、 -(CH2)5-、 -(CH2)6-、 -CO-、 -CONH-、 -CONH-CH2-、 -CONH-(CH2)2-、 -CONH-(CH2)3-、 -CONH-(CH2)4-、 -CONH-(CH2)5-、 -CONH-(CH2)6-、 -CON(CH3)-CH2-、 -CON(CH3)-(CH2)2-、 -CON(CH3)-(CH2)3-、 -CON(CH3)-(CH2)4-、 -CON(CH3)-(CH2)5-、 -CON(CH3)-(CH2)6-、 -CON(Ph)-CH2- (where Ph means phenyl), -CON(Ph)-(CH2)2- (where Ph means phenyl), -CON(Ph)-(CH2)3- (where Ph means phenyl), -CON(Ph)-(CH2)4- (where Ph means phenyl), -CON(Ph)-(CH2)5- (where Ph means phenyl), -CON(Ph)-(CH2)6- (where Ph means phenyl), -CONH-(CH2)2NH(CH2)3-、 -CONH-(CH2)6NH(CH2)3-、 -CH2O-CONH-(CH2)3-、 -CH2O-CONH-(CH2)6-、 -S-(CH2)3-、 -(CH2)2S(CH2)3-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、 -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10Si(CH3)2(CH2)2-, -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-, -C(O)O-(CH2)3-, -C(O)O-(CH2)6-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-, -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-, -OCH2-, -O(CH2)3-, -OCFHCF2-,

Chem.

Chem.

[0314] In yet another aspect, X A is, independently of each other, a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH2) z1 -. In the formula, x1, y1 and z1 are, independently of each other, integers from 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

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

[0316] The above-mentioned "divalent polar group" is not particularly limited, but includes -C(O)-, -C(=NR 19 )-, and -C(O)NR 19 -(in these formulas, 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, n-propyl, and these may be substituted by one or more fluorine atoms.

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

[0318] In addition, the above X A is such that the left side of each formula is bonded to R FA1 or R FA2 , and the right side is bonded to T X and T X '.

[0319] In yet another aspect, examples of X A include the following groups:

Chemical formula

Chemical formula

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

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

[0322] In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include [Chemical formula] and the like.

[0323] In this embodiment, X A can each independently be a group having a valence of 3 to 10.

[0324] In yet another embodiment, examples of X A include the following groups: [Chemical formula] [wherein, R 25 , R 26 and R 27 are each independently an organic group having a valence of 2 to 6, R 25 is bonded to at least one of R FA1 or R FA2 , and R 26 and R 27 are each bonded to at least one of R Si .]

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

[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 in the end or main chain of the hydrocarbon, and preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2-, etc. Here, R 36 are each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R 37 is N, O, or S, preferably N or O. R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 - or -R 45 -R 46 -. Here, R 45 are each independently an alkyl group having 1 to 6 carbon atoms. R 46 is N, O, or S, preferably O.

[0327] In this embodiment, X A can each independently be a 3- to 10-valent group.

[0328] In yet another embodiment, X A is as follows:

Chemical formula

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

[0330] X a For example, the following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (In the formula, X 121 ~X 124 are each independently H, F, OH, or -OSi(OR 121 )3 (In the formula, the three Rs 121 are each independently an alkyl group having 1 to 4 carbon atoms.) and the above X a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is bonded to CX 121 X 122 ). x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.) The group represented by is more preferable.

[0331] As the above X a1 , -O- or -C(=O)O- is preferable.

[0332] As the above X a , for example, the following formula: -(CF2) m11 -(CH2) m12 -O-(CH2) m13 - (wherein, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.) a group represented by -(CF2) m14 -(CH2) m15 -O-CH2CH(OH)-(CH2) m16 - (wherein, m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.) a group represented by -(CF2) m17 -(CH2) m18 - (wherein, m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.) a group represented by -(CF2) m19 -(CH2) m20 -O-CH2CH(OSi(OCH3)3)-(CH2) m21 - (wherein, m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3.) a group represented by, or -(CH2) m22 - (wherein, m22 is an integer of 1 to 3.) a group represented by is particularly preferred.

[0333] The above X a is not particularly limited, but specifically, -CH2-, -C2H4-, -C3H6-, -C4H8-, -C4H8-O-CH2-, -CO-O-CH2-CH(OH)-CH2-, -(CF2) n5 -(n5 is an integer of 0 to 4), -(CF2) n5 -(CH2) m5 -(n5 and m5 are each independently an integer of 0 to 4), -CF2CF2CH2OCH2CH(OH)CH2-, -CF2CF2CH2OCH2CH(OSi(OCH3)3)CH2- and the like can be mentioned.

[0334] In this embodiment, XA Each can 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 have a number average molecular weight of 5×10 2 ~1×10 5 It may have a number average molecular weight of. Among such ranges, it is preferable from the viewpoint of polymerization stability to have a number average molecular weight of preferably 2,000 or more, more preferably 2,500 or more as the lower limit, and preferably 32,000 or less, more preferably 12,000 or less as the upper limit. The number average molecular weight of the compound (II) is 19 a value measured by 19F-NMR.

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

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

[0339] Examples of the compound (II) include the compounds described in International Publication No. 2019 / 048394.

[0340] The content of the above polymer compound in the TFE-based polymer composition of the present disclosure is preferably 100 mass ppm or less, more preferably 10 mass ppm or less, still 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. The lower limit is not particularly limited and may be an amount less than the lower limit of quantification.

[0341] The content of the above polymer compound in the TFE-based polymer composition is determined by solid NMR measurement. In addition, the measurement methods of the respective polymers are described in International Publication No. 2014 / 099453, International Publication No. 2010 / 075497, International Publication No. 2010 / 075496, International Publication No. 2011 / 008381, International Publication No. 2009 / 055521, International Publication No. 1987 / 007619, Japanese Patent Application Laid-Open No. 61-293476, International Publication No. 2010 / 075494, International Publication No. 2010 / 075359, International Publication No. 2012 / 082454, International Publication No. 2006 / 119224, International Publication No. 2013 / 085864, International Publication No. 2012 / 082707, International Publication No. 2012 / 082703, International Publication No. 2012 / 082451, International Publication No. 2006 / 135825, International Publication No. 2004 / 067588, International Publication No. 2009 / 068528, Japanese Patent Application Laid-Open No. 2004-075978, Japanese Patent Application Laid-Open No. 2001-226436, International Publication No. 1992 / 017635, International Publication No. 2014 / 069165, Japanese Patent Application Laid-Open No. 11-181009, etc. As the measurement method of the content of the above polymer compound, the measurement methods of the respective polymers described therein can be used.

[0342] The TFE-based polymer composition of the present disclosure preferably contains substantially no moisture. Thereby, generation of gas and deterioration of the characteristics of the electrochemical device can be suppressed. Further, since the electrode active material and the solid electrolyte to be combined can be widely selected, it is advantageous in terms of the production process. Substantially no moisture means that the moisture content with respect to the above TFE-based polymer composition is 0.010% by mass or less. The above moisture content is preferably 0.005% by mass or less, more preferably 0.003% by mass or less, still more preferably 0.002% by mass or less, and even more preferably 0.001% by mass or less. The above moisture content is measured by the following method. Measure the mass of the TFE-based polymer composition before and after heating at 150 °C for 2 hours, and calculate according to the following formula. Take the sample three times, calculate each time, then find the average, and adopt the average value. Moisture content (% by mass) = [(mass (g) of the TFE-based polymer composition before heating) - (mass (g) of the TFE-based polymer composition after heating)] / (mass (g) of the TFE-based polymer composition before heating) × 100

[0343] The TFE-based polymer composition of the present disclosure preferably has a fibrillating ability. The fibrillating ability refers to the property of being easily fibrillated by a shearing force to form fibrils. Since the TFE-based polymer composition having a fibrillating ability can be paste-extruded and the TFE-based polymer composition not having a fibrillating ability cannot be paste-extruded, whether or not the TFE-based polymer composition has a fibrillating ability can be determined based on whether or not the composition can be paste-extruded. Specifically, it is determined by the following method. Mix 60 g of the TFE-based polymer composition with 12.3 g of a hydrocarbon oil (trade name: Isopar G (registered trademark), manufactured by ExxonMobil) as an extrusion aid in a polyethylene container for 3 minutes. Fill the cylinder of the extruder with the above mixture at room temperature (25 ± 2 °C), apply a load of 0.47 MPa to the piston inserted into the cylinder, and hold for 1 minute. Next, extrude from the 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. At this time, if the beads are broken and cannot be continuously extruded, it is judged that there is no fibrillating ability (paste extrusion is not possible), and if the beads are not broken and can be continuously extruded, it is judged that there is fibrillating ability (paste extrusion is possible).

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

[0345] The TFE-based polymer composition of the present disclosure preferably has an endothermic peak temperature of 333 °C or higher, more preferably 335 °C or higher, still more preferably 337 °C or higher, even more preferably 340 °C or higher, and preferably 350 °C or lower, more preferably 346 °C or lower, in that it can form a sizing sheet with even better strength. The above endothermic peak temperature is the temperature corresponding to the minimum point in the melting heat curve obtained by performing differential scanning calorimetry [DSC] on a TFE-based polymer composition having no heating history at a temperature of 300 °C or higher at a heating rate of 10 °C / min. When there are two or more minimum points in one melting peak, each is taken as the endothermic peak temperature.

[0346] The TFE-based polymer composition of the present disclosure preferably has a melting point of 315 °C or higher, more preferably 320 °C or higher, still more preferably 323 °C or higher, even more preferably 325 °C or higher, and preferably 335 °C or lower, more preferably 330 °C or lower, in that it can form a sizing sheet with even better strength. The melting point is the temperature corresponding to the minimum point in the heat of fusion curve obtained by performing differential scanning calorimetry [DSC] at a heating rate of 10 °C / min for a TFE-based polymer composition that has been heated to a temperature of 300 °C or higher.

[0347] The TFE-based polymer composition of the present disclosure preferably has a standard specific gravity (SSG) of 2.280 or less, more preferably 2.250 or less, still more preferably 2.220 or less, still more preferably 2.200 or less, still more preferably 2.190 or less, particularly preferably 2.180 or less, and most preferably 2.170 or less, in that it can form a composite sheet with even better strength. The above SSG is preferably also 2.130 or more. The above SSG is measured by the water displacement method in accordance with ASTM D 792 using a sample molded in accordance with ASTM D 4895 89.

[0348] The TFE-based polymer composition of the present disclosure preferably has a 1.0% mass loss temperature of 492 °C or higher, more preferably 493 °C or higher, still more preferably 494 °C or higher, still more preferably 495 °C or higher, and may be 550 °C or lower, in that its electrical properties are further improved. The above 1.0% mass loss temperature is the value measured by the following method. Weigh accurately approximately 10 mg of a TFE-based polymer composition that has no history of being heated to a temperature of 300 °C or higher, place it in a dedicated aluminum pan, and measure it with a TG·DTA (simultaneous differential thermal and thermogravimetric analyzer). The 1.0% mass loss temperature is the temperature corresponding to the point where the weight has decreased by 1.0 mass% when the aluminum pan is heated from 25 °C to 600 °C at a rate of 10 °C / min in an air atmosphere.

[0349] The TFE-based polymer composition of the present disclosure preferably has a 0.1% mass loss temperature of 400 °C or higher, more preferably 401 °C or higher, still more preferably 402 °C or higher, even more preferably 403 °C or higher, and may be 450 °C or lower in terms of further improving electrical properties. The above 0.1% mass loss temperature is a value measured by the following method. Weigh approximately 10 mg of a TFE-based polymer composition without a heating history at a temperature of 300 °C or higher, place it in a dedicated aluminum pan, and measure it with a TG·DTA (simultaneous differential thermal and thermogravimetric analyzer). The 1.0% mass loss temperature is the temperature corresponding to the point where the weight has decreased by 0.1 mass% when the temperature of the aluminum pan is raised from 25 °C to 600 °C at a rate of 10 °C / min in an air atmosphere.

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

[0351] The TFE-based polymer composition of the present disclosure may have an average secondary particle diameter of 350 μm or more, preferably 400 μm or more, more preferably 450 μm or more, and preferably 1000 μm or less, more preferably 900 μm or less, still more preferably 800 μm or less, even more preferably 700 μm or less, and particularly preferably 600 μm or less. The above average secondary particle diameter is measured in accordance with JIS K 6891.

[0352] The TFE-based 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, in terms of excellent handleability. The upper limit is not particularly limited, and it may be 0.70 g / ml. The above apparent density is measured in accordance with JIS K 6892.

[0353] The form of the TFE-based polymer composition of the present disclosure is not limited, but it is preferably in powder form in that it can be mixed with an electrode active material or a solid electrolyte without using a large amount of a dispersion medium. Note that the above TFE-based polymer composition may be in a form other than powder, for example, it may be a dispersion.

[0354] The TFE-based polymer composition of the present disclosure can be suitably produced by fluorinating a TFE-based polymer to be treated.

[0355] The TFE-based polymer to be treated can be suitably produced by a production method including, for example, step (A) of preparing an aqueous dispersion of a TFE-based polymer by emulsion polymerization, step (B) of coagulating the aqueous dispersion to obtain a wet powder, and step (C) of drying the wet powder.

[0356] Step (A) is preferably step (A1) of obtaining an aqueous dispersion of a TFE-based polymer by emulsion polymerizing TFE in an aqueous medium in the presence of an anionic fluorine-containing surfactant.

[0357] The emulsion polymerization in step (A1) can be carried out by a known method. For example, by carrying out the emulsion polymerization of the monomers necessary to form the TFE-based polymer in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator, an aqueous dispersion containing particles (primary particles) of the TFE-based polymer is obtained. In the above emulsion polymerization, a chain transfer agent, a buffer, a pH adjuster, a stabilization aid, a dispersion stabilizer, a radical scavenger, etc. may be used as necessary.

[0358] The above emulsion polymerization can be carried out, for example, in an aqueous medium in the presence of an anionic fluorine-containing surfactant and a polymerization initiator. For the above emulsion polymerization, an aqueous medium, the above anionic fluorine-containing surfactant, a monomer, and, if necessary, other additives are charged into a polymerization reactor, the contents of the reactor are stirred, and the reactor is maintained at a predetermined polymerization temperature. Then, a predetermined amount of a polymerization initiator is added to initiate the polymerization reaction. After the start of the polymerization reaction, a monomer, a polymerization initiator, a chain transfer agent, the surfactant, etc. may be additionally added according to the purpose.

[0359] The above polymerization initiator is not particularly limited as long as it can generate radicals in the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Further, polymerization can also be initiated as a redox in combination with a reducing agent or the like. The concentration of the above polymerization initiator is appropriately determined according to the type of monomer, the molecular weight of the target TFE-based polymer, and the reaction rate.

[0360] As the above 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 peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxy esters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, etc. Also, di(ω-hydroxy-dodecafluorooctanoyl) peroxide, di(ω-hydroxy-tetradecafluorooctanoyl) peroxide, di(ω-hydroxy-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di(ω-chloro-hexafluorobutyryl) peroxide, di(ω-chloro-decafluorohexanoyl) peroxide, di(ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydroxy-dodecafluorooctanoyl-ω-hydroxy-hexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydroxy-dodecafluorooctanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl) peroxide, di(trichlorooctafluorohexanoyl) peroxide, di(tetrachloroundecafluorooctanoyl) peroxide, di(pentachlorotetradecafluorodecanoyl) peroxide, di(undecachlorodotriacontapentafluorodocosanoyl) peroxide, and di[perfluoro(or fluorochloro)acyl] peroxides, etc. are listed as typical ones.

[0362] The water-soluble radical polymerization initiator may be a known water-soluble peroxide. For example, ammonium salts, potassium salts, sodium salts, such as persulfuric acid, perboric acid, perchloric acid, phosphoric acid, percarbonic acid, etc., t-butyl permaleate, t-butyl hydroperoxide, succinic peroxide, etc. may be mentioned. Among them, ammonium persulfate and succinic peroxide are preferred. Reducing agents such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.

[0363] The addition amount of the water-soluble radical polymerization initiator is not particularly limited, but it may be added all at once, sequentially, or continuously at the initial stage of polymerization in an amount such that the polymerization rate does not decrease significantly (for example, several ppm with respect to the water concentration) or more. The upper limit is in the range where the reaction temperature may be increased while removing the heat of polymerization reaction from the equipment surface. A more preferable upper limit is in the range where the heat of polymerization reaction can be removed from the equipment surface. In terms of easily obtaining the above-described physical properties, the addition amount of the polymerization initiator is preferably an amount corresponding to 0.1 ppm or more with respect to the aqueous medium, more preferably an amount corresponding to 1.0 ppm or more, and preferably an amount corresponding to 100 ppm or less, more preferably an amount corresponding to 10 ppm or less.

[0364] For example, when performing polymerization at a low temperature of 30°C or lower, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, ammonium cerium nitrate, bromates, etc. Examples of the reducing agent include sulfites, bisulfites, bromates, diimines, oxalic acid, etc. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the sulfite include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the combination of the redox initiator. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate.

[0365] As the redox initiator, it is preferable that the oxidizing agent is permanganic acid or its salt, persulfate, manganese triacetate, cerium(IV) salt, or bromic acid or its salt, and the reducing agent is a dicarboxylic acid or its salt, or diimine. More preferably, the oxidizing agent is permanganic acid or its salt, persulfate, or bromic acid or its salt, and the reducing agent is a dicarboxylic acid or its salt.

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

[0367] The redox initiator is particularly preferably a combination of an oxidizing agent that is a salt and a reducing agent that is a salt. For example, the oxidizing agent that is a salt is more preferably at least one selected from the group consisting of persulfate, permanganate, cerium(IV) salt, and bromate, even more preferably permanganate, and particularly preferably potassium permanganate. Also, the reducing agent that is a salt is more preferably at least one selected from the group consisting of oxalate, malonate, succinate, glutarate, and bromate, even more preferably oxalate, and particularly preferably ammonium oxalate.

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

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

[0370] When one of the above redox polymerization initiators is added first and the remaining one is added continuously at the initial stage of polymerization, it is preferable to gradually reduce the addition rate in terms of obtaining a TFE-based polymer with a low SSG, and it is more preferable to stop the addition during polymerization. The preferred time to stop the addition is before 20 to 40% by mass of all the TFE consumed in the polymerization reaction is consumed.

[0371] When using a redox initiator as the polymerization initiator, for the aqueous medium, the addition amount of the oxidizing agent is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, still more preferably 0.5 ppm or more, even more preferably 1 ppm or more, particularly preferably 5 ppm or more, and extremely preferably 10 ppm or more. Also, it is preferably 10000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and even more preferably 50 ppm or less. The addition amount of the reducing agent is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, still more preferably 3 ppm or more, even more preferably 5 ppm or more, particularly preferably 10 ppm or more. Also, it is preferably 10000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, and even more preferably 50 ppm or less. Also, when using a redox initiator in the above emulsion polymerization, the polymerization temperature is preferably 100 °C or lower, more preferably 95 °C or lower, and still more preferably 90 °C or lower. Also, it is preferably 10 °C or higher, more preferably 20 °C or higher, and still more preferably 30 °C or higher.

[0372] As the above polymerization initiator, a water-soluble radical polymerization initiator and a redox initiator are preferable in terms of easily obtaining each of the above physical properties.

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

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

[0375] For the purpose of adjusting the particle size, it is preferable to perform the above emulsion polymerization by adding a nucleating agent. It is preferable to add the nucleating agent before the start of the polymerization reaction. As the above nucleating agent, known ones can be used. For example, it is preferably at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents, and more preferably a nonionic surfactant.

[0376] Examples of the above fluoropolyether include perfluoropolyether (PFPE) acid or its salt. The above perfluoropolyether (PFPE) acid or its salt may have an arbitrary chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Also, two or more types of fluorocarbon groups may be present in the molecule. A typical structure has a repeating unit represented by the following formula: (-CFCF3-CF2-O-) n (-CF2-CF2-CF2-O-) n (-CF2-CF2-O-) n -(-CF2-O-) m (-CF2-CFCF3-O-) n -(-CF2-O-) m

[0377] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed in this literature, the above PFPE acid or its salt may have a carboxylic acid group or its salt at one end or both ends. The above PFPE acid or its salt may also have a sulfonic acid, phosphonic acid group or their salts at one end or both ends. Further, the above PFPE acid or its salt may have different groups at each end. For monofunctional PFPE, the other end of the molecule is usually perfluorinated, but may contain hydrogen or chlorine atoms. The above PFPE acid or its salt has at least two ether oxygens, preferably at least four ether oxygens, 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 above PFPE acid or its salt has a total of at least 15 carbon atoms. For example, the preferred minimum value of n or n + m in the above repeating unit structure is at least 5. Two or more of the above PFPE acids or their salts having an acid group at one end or both ends can be used in the production method of the present disclosure. The above PFPE acid or its salt preferably has a number average molecular weight of less than 6000 g / mol.

[0378] In terms of being able to further increase the molecular weight of the TFE-based polymer and improve the strength of the composite sheet, it is preferable to perform the above emulsion polymerization by adding a radical scavenger or a decomposer of the polymerization initiator. The above radical scavenger or decomposer of the polymerization initiator is preferably added after the start of the polymerization reaction, preferably before 10% by mass or more, preferably 20% by mass or more of all the TFE consumed in the polymerization reaction is polymerized, and also preferably before 50% by mass or less, preferably 40% by mass or less is polymerized. When performing the pressure release and re-pressurization described later, it is preferably added thereafter.

[0379] As the radical scavenger, a compound that does not have a restart ability after addition or chain transfer to free radicals in the polymerization system is used. Specifically, a stable radical that easily undergoes a chain transfer reaction with a primary radical or a growing radical and then does not react with a monomer is generated, or a compound having a function of easily undergoing an addition reaction with a primary radical or a growing radical to generate a stable radical is used. What is generally called a chain transfer agent is characterized by its activity in terms of a chain transfer constant and a restart efficiency. Among chain transfer agents, those with a restart efficiency of almost 0% are called radical scavengers. The radical scavenger can also be, for example, a compound in which the chain transfer constant with TFE at the polymerization temperature is larger than the polymerization rate constant and the restart efficiency is substantially 0%. "The restart efficiency is substantially 0%" means that the generated radicals are converted into stable radicals by the radical scavenger. Preferably, it is a compound in which the chain transfer constant (Cs) (= chain transfer rate constant (kc) / polymerization rate constant (kp)) with TFE at the polymerization temperature is larger than 0.1. For the above compound, it is more preferable that the chain transfer constant (Cs) is 0.5 or more, still more preferable that it is 1.0 or more, even more preferable that it is 5.0 or more, and particularly preferable that it is 10 or more.

[0380] As the radical scavenger, for example, at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N - diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl2) is preferable. Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m - or p - salicylic acid, gallic acid, naphthol, and the like. Examples of the unsubstituted phenol include о -, m - or p - nitrophenol, о -, m - or p - aminophenol, p - nitrosophenol, and the like. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, naphthoresorcinol, and the like. Examples of the aromatic amines include o-, m- or p-phenylenediamine, benzidine and the like. Examples of the quinone compounds include o-, m- or p-benzoquinone, 1,4-naphthoquinone, alizarin and the like. Examples of the thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN) and the like. Among the above radical scavengers, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

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

[0382] The decomposer of the above polymerization initiator may be any compound that can decompose 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 the sulfite include sodium sulfite and ammonium sulfite. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate. From the viewpoint of moderately reducing the standard specific gravity, the addition amount of the above decomposer is preferably an amount corresponding to 3 to 500% (molar basis) of the initiator concentration. A more preferable lower limit is 10% (molar basis), and even more preferably 15% (molar basis). A more preferable upper limit is 400% (molar basis), and even more preferably 300% (molar basis).

[0383] The above emulsion polymerization may be carried out in the presence of 5 to 500 ppm of dicarboxylic acid with respect to the aqueous medium in order to reduce the amount of coagulum generated during the polymerization, and it is preferably carried out in the presence of 10 to 200 ppm of dicarboxylic acid. If the above dicarboxylic acid is too little with respect to the aqueous medium, there is a possibility that a sufficient effect cannot be obtained, and if it is too much, a chain transfer reaction may occur and the resulting polymer may have a low molecular weight. More preferably, the above dicarboxylic acid is 150 ppm or less. The above dicarboxylic acid may be added before the start of the polymerization reaction or during the polymerization.

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

[0385] In the above emulsion polymerization, the polymerization temperature and the polymerization pressure are appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, and the reaction rate. Usually, the polymerization temperature is 5 to 150 °C, preferably 10 °C or higher, more preferably 30 °C or higher, and even more preferably 50 °C or higher. Also, more preferably, it is 120 °C or lower, and even more preferably 100 °C or lower. The polymerization pressure is 0.05 to 10 MPaG. More preferably, the polymerization pressure is 0.3 MPaG or higher, and even more preferably 0.5 MPaG or higher. Also, more preferably, it is 5.0 MPaG or lower, and even more preferably 3.0 MPaG or lower.

[0386] When using VDF as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the concentration of VDF 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. The above 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 above VDF concentration may be maintained until the end of the polymerization reaction, or pressure reduction may be carried out during the process. VDF is preferably charged all at once before the start of polymerization, but a part thereof may be added continuously or intermittently after the start of polymerization.

[0387] When using VDF as the modified monomer, in the above emulsion polymerization, after charging VDF into the polymerization vessel, it is preferable not to carry out pressure reduction until the polymerization is completed. Thereby, VDF can be left in the system until the end of polymerization, and the strength of the composite sheet using the obtained TFE-based polymer can be further increased.

[0388] When using HFP as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, the concentration of HFP in the gas in the reactor at the start of polymerization (when the initiator is added) is preferably 0.01 to 3.0 mol%. Further, when 40% by mass of all the TFE consumed in the polymerization reaction is polymerized, the concentration of HFP in the gas in the reactor is preferably greater than 0 mol% and 0.2 mol% or less. The above HFP concentration is preferably maintained until the end of the polymerization reaction. HFP may be charged all at once before the start of polymerization, or a part thereof may be charged before the start of polymerization and continuously or intermittently added after the start of polymerization. By allowing HFP to remain until the end of the polymerization reaction, although the strength of the composite sheet using the obtained TFE-based polymer is high, the extrusion pressure decreases.

[0389] When using HFP as the modified monomer, in the above emulsion polymerization, in terms of further improving the strength of the coating sheet using the obtained TFE-based polymer, it is preferable to depressurize before 5 to 40% by mass of the total TFE consumed in the polymerization reaction is polymerized, and then repressurize only with TFE. The above depressurization is preferably carried out so that the pressure in the reactor becomes 0.2 MPaG or less, more preferably so that it becomes 0.1 MPaG or less, and even more preferably so that it becomes 0.05 MPaG or less. Also, it is preferably carried out so that it becomes 0.0 MPaG or more. Further, the above depressurization and repressurization may be carried out multiple times. The depressurization may be carried out to a reduced pressure using a vacuum pump.

[0390] When using CTFE as the modified monomer, in the above emulsion polymerization, in terms of easily obtaining each of the above physical properties, it is preferable that the CTFE concentration in the gas in the reactor at the start of polymerization (when the initiator is added) is 0.001 mol% or more, and more preferably 0.01 mol% or more. The above concentration is also preferably 3.0 mol% or less, and more preferably 1.0 mol% or less. The above CTFE concentration may be maintained until the end of the polymerization reaction, or depressurization may be carried out during the process. CTFE is preferably charged all at once before the start of polymerization, but a part may be added continuously or intermittently after the start of polymerization.

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

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

[0393] The hydrocarbon surfactant preferably has 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted at all with fluorine atoms) of the hydrogen atoms bonded to carbon atoms substituted with fluorine atoms.

[0394] Step (A2) preferably includes a step of performing emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of a specific hydrocarbon surfactant, and a step of continuously adding the specific hydrocarbon surfactant in the above step.

[0395] Continuously adding a specific hydrocarbon surfactant means, for example, adding the specific hydrocarbon surfactant not all at once, but over time, without interruption or in portions. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxy group), or a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxy group) to radical treatment or oxidation treatment. The above radical treatment may be any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxy group). For example, 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 charged, stirred for a certain period of time, and then the reactor is depressurized until it reaches atmospheric pressure and cooled. The above oxidation treatment is a treatment in which an oxidizing agent is added to a hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxy group). Examples of the oxidizing agent include oxygen, ozone, hydrogen peroxide solution, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, and the like. By the above production method, a TFE-based polymer having a molecular weight equivalent to that of a production method using a conventional fluorine-containing surfactant can be produced without using a conventional fluorine-containing surfactant.

[0396] In the above manufacturing method, in the step of continuously adding the specific hydrocarbon surfactant, it is preferable that the addition of the hydrocarbon surfactant to the aqueous medium is started when the solid content of the TFE-based polymer formed in the aqueous medium is less than 0.60% by mass. When it is 0.5% by mass or less, it is preferable that the addition of the specific hydrocarbon surfactant to the aqueous medium is started. It is more preferable to start adding the specific hydrocarbon surfactant when the solid content is 0.3% by mass or less, still more preferable to start adding when it is 0.2% by mass or less, even more preferable to start adding when it is 0.1% by mass or less, and particularly preferable to start adding together with the start of polymerization. The solid content is the concentration with respect to the total of the aqueous medium and the TFE-based polymer.

[0397] In the step of continuously adding the specific hydrocarbon surfactant, the addition amount of the specific hydrocarbon surfactant is preferably 0.01 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.05% by mass, a still more preferable lower limit is 0.1% by mass, a more preferable upper limit is 5% by mass, and a still more preferable upper limit is 1% by mass.

[0398] In the step of performing emulsion polymerization of only tetrafluoroethylene or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of the specific hydrocarbon surfactant, it is preferable that the amount of the specific hydrocarbon surfactant is large, and it is preferably 0.0001 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If it is less than 0.0001% by mass, the dispersing power may be insufficient, and if it exceeds 10% by mass, an effect commensurate with the amount cannot be obtained, and instead, the polymerization rate may decrease or the reaction may stop. The amount of the specific hydrocarbon surfactant is appropriately determined according to the type of monomer used, the molecular weight of the target TFE-based polymer, etc.

[0399] As the above-mentioned specific hydrocarbon surfactant, there is a formula: R-X (wherein, R is a fluorine-free organic group having 1 to 2000 carbon atoms and having one or more carbonyl groups (excluding the carbonyl group in the carboxy group), and X is -OSO3X 1 , -COOX 1 or -SO3X 1 (X 1 is H, a metal atom, NR 1 4, imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 1 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.)) The surfactant represented by is preferred. R preferably has 500 or less carbon atoms, more preferably 100 or less carbon atoms, still more preferably 50 or less carbon atoms, and still more preferably 30 or less carbon atoms. As the above-mentioned specific hydrocarbon surfactant, there is the following formula (a):

Chemical formula

Chemical formula

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

[0401] In formula (a), R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Further, when the alkyl group has 2 or more carbon atoms, the terminal of the alkyl group may contain the carbonyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the alkyl group. In addition, when the number of carbon atoms of the above alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring and the like can be mentioned. R 1a In, a divalent heterocyclic ring may be inserted between two carbon atoms, or a divalent heterocyclic ring may be located at the end and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the end of the above alkyl group.

[0402] In this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0403] The above alkyl group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. As the above monovalent organic group containing an ester bond, the group represented by the formula: -O-C(=O)-R 101a (wherein R 101a is an alkyl group) can be mentioned. The above alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0404] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group. R 2a and R 3ais preferably, independently, a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms. R 2a and R 3a The alkylene group constituting is preferably free of a carbonyl group.

[0405] The alkylene group may have a hydrogen atom bonded to a carbon atom substituted by a functional group, for example, may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 102a (wherein R 102a is an alkyl group). The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, may have 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

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

[0407] In formula (a), X a is H, a metal atom, NR 4a 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, and R 4ais H or an organic group (preferably an organic group not containing fluorine). The four Rs 4a may be the same or different. As the organic group in R 4a , an alkyl group is preferred. As R 4a , H or an organic group having 1 to 10 carbon atoms is preferred, H or an organic group having 1 to 4 carbon atoms is more preferred, and H or an alkyl group having 1 to 4 carbon atoms is still more preferred. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferred. X a is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4a 4. Since it is easily soluble in water, H, Na, K, Li or NH4 is more preferred. Since it is still more easily soluble in water, Na, K or NH4 is still more preferred. Since Na or NH4 is particularly preferred. Since removal is easy, NH4 is most preferred. When X a is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in the TFE-based polymer or the final product.

[0408] Examples of the surfactant (a) include the following surfactants. In each formula, X a is as described above.

[0409]

Chemical formula

[0410]

Chemical formula

[0411]

Chemical formula

[0412]

Chemical formula

[0413] [Chemistry]

[0414] [Chemistry]

[0415] [Chemistry]

[0416] [Chemistry]

[0417] The surfactant (a) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

[0419] In formula (b), R 1b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the above alkyl group has 3 or more carbon atoms, it can also contain a monovalent or divalent heterocyclic ring, or can form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring etc. are mentioned. In R 1b , a divalent heterocyclic ring may be inserted between two carbon atoms, a divalent heterocyclic ring may be located at the end and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the end of the above alkyl group.

[0420] In this specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the above heterocyclic ring.

[0421] R 1bExamples of the substituent that the alkyl group may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group, with a methyl group and an ethyl group being particularly preferred.

[0422] R 1b The alkyl group preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The alkyl group preferably has no substituents.

[0423] R 1b Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents, or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents. Even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. Particularly preferably, it is a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably, it is a methyl group (-CH3).

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

[0425] R 2b and R 4bAs the above-mentioned substituent, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0426] R 2b and R 4b The above-mentioned alkyl group as such preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above-mentioned alkyl group preferably has no substituents.

[0427] R 2b and R 4b As the above-mentioned alkyl group as such, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0428] R 2b and R 4b As such, independently, H or a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is preferable, H or a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is still more preferable, and H is particularly preferable.

[0429] In formula (b), R 3b is an alkylene group having 1 to 10 carbon atoms that may have substituents. R 3bWhen multiple are present, 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 of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

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

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

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

[0434] In formula (b), p and q are each independently an integer of 0 or more. As p, an integer of 0 to 10 is preferable, and 0 or 1 is more preferable. As q, an integer of 0 to 10 is preferable, and an integer of 0 to 5 is more preferable.

[0435] n, p, and q preferably have a total that is an integer of 5 or more. More preferably, the total of n, p, and q is an integer of 8 or more. The total of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0436] In formula (b), X b is H, a metal atom, NR 5b 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 5b is H or an organic group (preferably an organic group not containing fluorine). The four Rs 5b may be the same or different. As the organic group for R 5b , an alkyl group is preferable. As R 5b , H or an organic group having 1 to 10 carbon atoms is preferable, H or an organic group having 1 to 4 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is still more preferable. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K, or Li is preferable. X b is a metal atom or NR 5b 4 (R 5b is as described above) may be. X b is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 5b 4. Since it is easily soluble in water, H, Na, K, Li, or NH4 is more preferable. Since it is even more easily soluble in water, Na, K, or NH4 is still more preferable. Na or NH4 is particularly preferable. Since it is easily removable, NH4 is most preferable. When X b is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for a metal component to remain in the TFE-based polymer or the final product.

[0437] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-*, or -CO- (provided that the carbonyl groups contained in -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b CO-B- are excluded).), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The above alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6b is preferably H or a methyl group. * indicates the side bonded to -OSO3X b in the formula.

[0438] L is preferably a single bond.

[0439] As the surfactant (b), the following formula:

Chemical formula

[0440] Examples of the surfactant (b) include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na and the like can be mentioned.

[0441] The surfactant (b) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

[0443] In formula (c), R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the above alkyl group has 3 or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. Also, when the above alkyl group has 2 or more carbon atoms, the above carbonyl group can also be included at the end of the above alkyl group. That is, an acyl group such as an acetyl group represented by CH3-C(=O)- is also included in the above alkyl group. In addition, when the above alkyl group has 3 or more carbon atoms, it can also contain a monovalent or divalent heterocyclic ring or can form a ring. As the above heterocyclic ring, an unsaturated heterocyclic ring is preferable, and an oxygen-containing unsaturated heterocyclic ring is more preferable. For example, a furan ring and the like can be mentioned. R 1cIn this case, a divalent heterocyclic ring may be inserted between two carbon atoms, or the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, or a monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0444] In the present specification, the "number of carbon atoms" of the above alkyl group shall include the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocyclic ring. For example, the group represented by CH3-C(=O)-CH2- has 3 carbon atoms, the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and the group represented by CH3-C(=O)- has 2 carbon atoms.

[0445] The above alkyl group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: -O-C(=O)-R 101c (wherein R 101c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0446] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group. R 2c and R 3c are independently preferably a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms. R 2c and R 3cThe above-mentioned alkylene group constituting it preferably does not contain a carbonyl group.

[0447] The above-mentioned alkylene group may have a hydrogen atom bonded to a carbon atom substituted by a functional group. For example, it may be substituted by a hydroxy group (-OH) or a monovalent organic group containing an ester bond (preferably an organic group not containing fluorine), but it is preferably not substituted by any functional group. Examples of the above-mentioned monovalent organic group containing an ester bond include the group represented by the formula: -O-C(=O)-R 102c (In the formula, R 102c is an alkyl group). Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkylene group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0448] R 1c 、R 2c and R 3c have a total carbon number of 5 or more. As the total carbon number, 7 or more is preferable, 9 or more is more preferable, 20 or less is preferable, 18 or less is more preferable, and 15 or less is even more preferable. R 1c 、R 2c and R 3c Any two of them may be bonded to each other to form a ring.

[0449] In formula (c), in the formula, A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and R 4c is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different. ). R 4cAs the organic group in [context not clear], an alkyl group is preferred. R 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 still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K, or Li is preferred. X c is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 4c 4. Since it is easily soluble in water, H, Na, K, Li, or NH4 is more preferred. Since it is even more easily soluble in water, Na, K, or NH4 is still more preferred. Na or NH4 is particularly preferred. Since it is easy to remove, NH4 is most preferred. When X c is NH4, the surfactant has excellent solubility in the aqueous medium, and it is difficult for metal components to remain in the TFE-based polymer or the final product.

[0450] Examples of the above surfactant (c) include the following surfactants. In each formula, A c is as described above.

[0451]

Chemical formula

[0452]

Chemical formula

[0453]

Chemical formula

[0454]

Chemical formula

[0455]

Chemical formula

[0456] [Chem.]

[0457] [Chem.]

[0458] [Chem.]

[0459] The surfactant (c) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

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

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

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

[0464] R 1d The alkyl group as such preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The alkyl group preferably has no substituents.

[0465] R 1d Preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that may have substituents or a cyclic alkyl group having 3 to 10 carbon atoms that may have substituents, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group, still more preferably a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents, even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0466] In formula (d), R 2d and R 4d are each independently H or a substituent. A plurality of R 2d and R 4d may be the same or different from each other.

[0467] R 2d and R 4dAs the above-mentioned substituent, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group is preferable, and a methyl group or an ethyl group is particularly preferable.

[0468] R 2d and R 4d As the above-mentioned alkyl group, it is preferably free of a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the above-mentioned alkyl group may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms. The above-mentioned alkyl group preferably has no substituents.

[0469] R 2d and R 4d As the above-mentioned alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is still more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0470] R 2d and R 4d Independently, H or a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group is preferable, H or a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents is more preferable, H, a methyl group (-CH3) or an ethyl group (-C2H5) is still more preferable, and H is particularly preferable.

[0471] In formula (d), R 3d is an alkylene group having 1 to 10 carbon atoms which may have a substituent. R 3dWhen multiple are present, 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 carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated 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 even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and even more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

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

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

[0476] In formula (d), p and q are independently an integer of 0 or more. p is preferably an integer of 0 to 10, and more preferably 0 or 1. q is preferably an integer of 0 to 10, and more preferably an integer of 0 to 5.

[0477] n, p, and q are preferably integers whose sum is 6 or more. More preferably, the sum of n, p, and q is an integer of 8 or more. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

[0478] In formula (d), A d is -SO3X d or -COOX d (where X d is H, a metal atom, NR 5d 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, and R 5d is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.). R 5d The organic group in is preferably an alkyl group. R 5d is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the above metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K, or Li is preferred. X d is a metal atom or NR 5d 4 (R 5d is as described above). X d is preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 5d 4. Since it is easily soluble in water, H, Na, K, Li, or NH4 is more preferred. Since it is even more easily soluble in water, Na, K, or NH4 is still more preferred. Na or NH4 is particularly preferred. Since it is easily removable, NH4 is most preferred. When X d is NH4, the surfactant has excellent solubility in an aqueous medium, and it is difficult for metal components to remain in the TFE-based polymer or the final product.

[0479] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d-B-*, -NR 6d CO-B-*, or -CO- (however, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d excluding the carbonyl group contained in CO-B-.), where B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The above alkylene group preferably has 1 to 5 carbon atoms. Also, the above R 6d is more preferably H or a methyl group. * refers to the side bonded to A in the formula. d

[0480] L is preferably a single bond.

[0481] Examples of the surfactant (d) include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, ​CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2SO3Na, CH3C(O)CH2CH2SO3Na, CH3C(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na etc. can be mentioned.

[0482] Surfactant (d) can be produced, for example, by the production method described in International Publication No. 2020 / 022355.

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

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

[0485] R 1eExamples of the substituent that the alkyl group may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxy group, with a methyl group or an ethyl group being particularly preferred.

[0486] R 1e The alkyl group preferably does not contain a carbonyl group. Up to 75% of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted by a halogen atom, up to 50% may be substituted by a halogen atom, and up to 25% may be substituted by a halogen atom, but it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom. The alkyl group preferably has no substituents.

[0487] R 1e Examples include a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms that may have a substituent. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group. Even more preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms that has no substituents, and even more preferably, it is a linear or branched alkyl group having 1 to 3 carbon atoms that has no substituents. A methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0488] Examples of the monovalent substituent include a group represented by the general formula: -Y e -R 6e a group represented by the general formula: -X e -A e a group represented by, -H, an alkyl group of C 1-20 which may have a substituent, -NH2, -NHR 9e (R 9e is an organic group (preferably an organic group that does not contain 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 number of carbon atoms of the alkyl group is preferably 1 to 10.

[0489] R 9e As 1-10 an alkyl group of C 1-10 or an alkylcarbonyl group of C 1-4 is preferred, and an alkyl group of C 1-4 or an alkylcarbonyl group of C

[0490] In the formula, X e represents, in each occurrence, the same or different divalent linking group or a bond. R 6e When it 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 As 8e a divalent linking group containing at least one bond selected from the group consisting of -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -O-S(=O)2-, -CONR 8e -, -NR 1-10 CO- and an alkylene group of C 8e or a bond is preferred. R

[0492] R 8e The organic group in is preferably an alkyl group. R 8e As 1-10 is preferably H or an organic group of C 1-4 is more preferably H or an organic group of C 1-4 is still more preferably an alkyl group of C

[0493] In formula (e), A e is, in each occurrence, the same or different, -COOM e , -SO3M e or -OSO3M e (M e is H, a metal atom, NR 7e 4, an optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, R 7e is H or an organic group (preferably an organic group not containing fluorine). The four Rs 7e may be the same or different.). In formula (e), A e being -COOM e is one of the preferred embodiments.

[0494] As the organic group in R 7e , an alkyl group is preferred. As R 7e , H or a C 1-10 organic group is preferred, H or a C 1-4 organic group is more preferred, and H or a C 1-4 alkyl group is even more preferred. Examples of the above metal atom include an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., and Na, K or Li is preferred.

[0495] As M e , H, a metal atom or NR 7e 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7e 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, Na, K or NH4 is even more preferably, Na or NH4 is particularly preferred, and NH4 is most preferred.

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

[0497] Y e As, a divalent linking group selected from the group consisting of a bond, -O-, -COO-, -OCO-, -CONR 8e - and -NR 8e 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 is preferably an alkyl group. R 8e As, an organic group of H or C 1-10 is preferred, an organic group of H or C 1-4 is more preferred, an organic group of H or C 1-4 alkyl group is still more preferred, and H is still more preferred.

[0499] In formula (e), R 6e represents, in each occurrence, the same or different, an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms. The above R 6e The carbon number of the organic group (preferably an organic group not containing fluorine) is preferably 2 to 20, more preferably 2 to 10.

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

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

[0502] As the organic group in R 8e , an alkyl group is preferred. As R 8e , H or a C 1-10 organic group is preferred, H or a C 1-4 organic group is more preferred, H or a C 1-4 alkyl group is even more preferred, and H is even more preferred.

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

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

[0505] In formula (e), at least one of R 2e and R 5e is a group represented by the general formula: -X e -A e wherein the A e is -COOM e which is also one of the preferred embodiments.

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

[0507] General formula (e-1):

Chemical formula

[0508] General formula (e-2):

Chemical formula

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

[0510] General formula: -X e -A e Examples of the group represented by are -COOM e , -R 12e COOM e , -SO3M e , -OSO3M e , -R 12e SO3M e , -R 12e OSO3M e , -OCO-R 12e -COOM e , -OCO-R 12e -SO3M e , -OCO-R 12e -OSO3M e , -COO-R 12e -COOM e , -COO-R 12e -SO3M e , -COO-R 12e -OSO3M e , -CONR 8e -R 12e -COOM e , -CONR 8e -R 12e -SO3M e , -CONR 8e -R 12e -OSO3M e , -NR 8e CO-R 12e -COOM e , -NR 8e CO-R 12e -SO3M e , -NR 8e CO-R 12e -OSO3M e , -OS(=O)2-R 12e -COOM e , -OS(=O)2-R 12e -SO3M e or -OS(=O)2-R 12e -OSO3M e (In the formula, R 8e and M e As stated above. R 12e is C 1-10 An alkylene group represented by the formula: is preferred. Above R 12e The alkylene group may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

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

[0512] In the formula, R 4e and R 5e are, independently, preferably H or an alkyl group of C 1-4 . The above-mentioned alkyl groups of R 4e and R 5e may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, or may have 25% or less substituted by halogen atoms, but are preferably non-halogenated alkyl groups containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0513] As R 3e in the general formula (e-1), H or an optionally substituted alkyl group of C 1-20 is preferred, an alkyl group of C 1-20 without substituents is more preferred, and H is even more preferred. The above-mentioned alkyl groups of R 3e may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, may have 50% or less substituted by halogen atoms, or may have 25% or less substituted by halogen atoms, but are preferably non-halogenated alkyl groups containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0514] R in the general formula (e-3) 2e is preferably H, OH, or an optionally substituted C 1-20 alkyl group, more preferably H, OH, or an unsubstituted C 1-20 alkyl group, and even more preferably H or OH. The above R 2e alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted by halogen atoms, 50% or less substituted by halogen atoms, or 25% or less substituted by halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

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

[0516] The above specific hydrocarbon surfactant is also preferably a carboxylic acid type hydrocarbon surfactant. The above carboxylic acid type 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 by an inorganic cation (for example, a metal atom, ammonium, etc.). For example, among the above-mentioned specific hydrocarbon surfactants, a hydrocarbon surfactant having a carboxy group or a group in which the hydrogen atom of the carboxy group is substituted by an inorganic cation can be used. The above carboxylic acid type hydrocarbon surfactant preferably has a ratio of hydrogen atoms bonded to carbon atoms substituted by fluorine atoms of 50% or less, more preferably 25% or less, even more preferably 10% or less, and most preferably 0% (not substituted by fluorine atoms at all).

[0517] As the above carboxylic acid type hydrocarbon surfactant, preferably, at least one selected from the group consisting of the surfactant (c) represented by the above formula (c) and the surfactant (d) represented by the above formula (d), those having a carboxy group (-COOH) or a group in which the hydrogen atom of the carboxy group is substituted by an inorganic cation (for example, a metal atom, ammonium, etc.) are preferred.

[0518] It is also preferable that the specific hydrocarbon surfactant is a sulfonic acid type hydrocarbon surfactant. The sulfonic acid type hydrocarbon surfactant is not limited as long as it has a -SO3H group, -OSO3H group, or a group in which a hydrogen atom of these groups is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.). For example, among the specific hydrocarbon surfactants described above, a hydrocarbon surfactant having a -SO3H group, -OSO3H group, or a group in which a hydrogen atom of these groups is substituted with an inorganic cation can be used. It is preferable that the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the sulfonic acid type hydrocarbon surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0519] The TFE-based polymer composition of the present disclosure can be efficiently produced by using at least one of the specific hydrocarbon surfactants. Further, the TFE-based polymer composition of the present disclosure may be produced by simultaneously using two or more of the specific hydrocarbon surfactants, or may be produced by simultaneously using a compound having other surfactant properties other than the specific hydrocarbon surfactant as long as it has volatility or can remain in a molded body made of a TFE-based polymer or the like.

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

[0521] The compound having other surfactant properties may be a surfactant having a hydrophilic part and a hydrophobic part on the same molecule, for example, a hydrocarbon surfactant. These may be cationic, nonionic or anionic. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above compound is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0522] Cationic surfactants usually have a positively charged hydrophilic moiety such as alkylated ammonium bromide and other alkylated ammonium halides, and a hydrophobic moiety such as a long-chain fatty acid. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above cationic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0523] Anionic surfactants usually have a hydrophilic moiety such as carboxylate, sulfonate or sulfate, and a hydrophobic moiety which is a long-chain hydrocarbon moiety such as alkyl. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above anionic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0524] Nonionic surfactants usually do not contain a charged group and have a hydrophobic moiety which is a long-chain hydrocarbon. The hydrophilic moiety of nonionic surfactants contains water-soluble functional groups such as a chain of ethylene ethers derived from polymerization with ethylene oxide. Preferably, the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms in the above nonionic surfactant is 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted with fluorine atoms at all).

[0525] Examples of nonionic surfactants Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, glycerol ester, and derivatives thereof.

[0526] Specific examples of polyoxyethylene alkyl ether: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, etc.

[0527] Specific examples of polyoxyethylene alkyl phenyl ether: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, etc.

[0528] Specific examples of polyoxyethylene alkyl ester: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, etc.

[0529] Specific examples of sorbitan alkyl ester: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.

[0530] Specific examples of polyoxyethylene sorbitan alkyl ester: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, etc.

[0531] Specific examples of glycerol ester: glycerol monomyristate, glycerol monostearate, glycerol monooleate, etc.

[0532] Specific examples of the above derivatives: polyoxyethylene alkylamine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, etc.

[0533] The above-mentioned ether and ester may have an HLB value of 10 to 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.), Tergitol (registered trademark) L series manufactured by Dow Chemical Company; Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)), Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10, etc.) manufactured by BASF.

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

[0536] Other compounds having surfactant properties include R-L-M (wherein R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when having 3 or more carbon atoms, may contain a monovalent or divalent heterocyclic ring or may form a ring; L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - ; and M is H, a metal atom, NR 5 4 (R 5 may be the same or different, and is H or an organic group (preferably an organic group not containing fluorine)), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate. ), and anionic surfactants represented thereby are also included. R5 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, those represented by CH3-(CH2) n -L-M (wherein n is an integer of 6 to 17. L and M are the same as above) can be mentioned. A mixture in which R is an alkyl group having 12 to 16 carbon atoms and L-M is a sulfate or sodium dodecyl sulfate (SDS) can also be used. As other compounds having surfactant properties, R 6 (-L-M)2 (wherein R 6 is a linear or branched alkylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR 5 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent, R 5 is H or an organic group (preferably an organic group not containing fluorine), -ArSO3 - is an arylsulfonate. ) Also included are anionic surfactants represented by As other compounds having surfactant properties, R 7 (-L-M)3 (wherein R 7 is a linear or branched alkylidine group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylidine group having 3 or more carbon atoms which may have a substituent. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, NR5 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 5 is H or an organic group (preferably an organic group not containing fluorine). -ArSO3 - is an aryl sulfonate. ) Also included are anionic surfactants represented by

[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 siloxane surfactants includes a distinct hydrophobic part and a hydrophilic part. The hydrophobic part contains one or more dihydrocarbyl siloxane units, where the substituents on the silicon atom are completely hydrocarbons. In the sense that when the carbon atoms of the hydrocarbyl group can be substituted by a halogen such as fluorine and are completely substituted by hydrogen atoms, these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituents on the carbon atoms of the hydrocarbyl group are hydrogen. Preferably, the above siloxane surfactant has a proportion of hydrogen atoms bonded to carbon atoms substituted by fluorine atoms of 50% or less, more preferably 25% or less, still more preferably 10% or less, and most preferably 0% (not substituted by fluorine atoms at all).

[0538] Siloxane hydrocarbon surfactants are also disclosed in U.S. Patent No. 6,841,616.

[0539] Examples of siloxane-based anionic hydrocarbon surfactants include SilSense TM PE-100 silicone, SilSense TM CA-1 silicone, etc. available from Noveon (registered trademark) Consumer Specialties of Lubrizol Advanced Materials, Inc.

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

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

[0542] Other compounds having surfactant properties are preferably anionic hydrocarbon surfactants. As the anionic hydrocarbon surfactants, those described above can be adopted, and for example, the following hydrocarbon surfactants can be preferably adopted.

[0543] Examples of the above anionic hydrocarbon surfactants include, for example, the following formula (α): R 100 -COOM (α) (In the formula, R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 101 4, an imidazolium optionally having a substituent, a pyridinium optionally having a substituent, or a phosphonium optionally having a substituent, and R 101 is H or an organic group (preferably an organic group not containing fluorine), and they may be the same or different.) The compound (α) represented by the formula is exemplified. As the organic group of R 101 , an alkyl group is preferable. R 101is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant properties, R 100 preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms. Also, from the viewpoint of water solubility, R 100 preferably has 29 or fewer carbon atoms, more preferably 23 or fewer carbon atoms. Examples of the metal atom of M include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. M is preferably H, a metal atom, or NR 101 4, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 101 4, still more preferably H, Na, K, Li, or NH4, even more preferably Na, K, or NH4, particularly preferably Na or NH4, and most preferably NH4.

[0544] Examples of the compound (α) include an anionic surfactant represented by R 102 -COOM (wherein R 102 is a linear or branched alkyl group, alkenyl group, alkylene group, or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group, or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When having 3 or more carbon atoms, they may contain a monovalent or divalent heterocyclic ring or may form a ring. M is the same as above). Specifically, those represented by CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28. M is the same as above) are included.

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

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

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

[0548] Examples of the above compound (α) include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, 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, osbond acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid, and salts thereof. Particularly, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof is preferable. Examples of the above salt include those in which the hydrogen of the carboxy group is a metal atom of the above formula M, NR 11 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, but is not particularly limited.

[0549] Examples of the above anionic hydrocarbon surfactant also include, for example, the following formula (β): R 100 -SO3M (β) (In the formula, R 100 is a monovalent organic group containing one or more carbon atoms (preferably an organic group not containing fluorine). M is H, a metal atom, NR 1014. An optionally substituted imidazolium, an optionally substituted pyridinium or an optionally substituted phosphonium, where R 101 is H or an organic group (preferably an organic group not containing fluorine), which may be the same or different. The compound (β) represented by ) is also included. R 101 As the organic group, an alkyl group is preferred. R 101 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant properties, the number of carbon atoms of R 100 is preferably 2 or more, more preferably 3 or more. Also, from the viewpoint of water solubility, the number of carbon atoms of R 100 is preferably 29 or less, more preferably 23 or less. Examples of the metal atom of M include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred. As M, H, a metal atom or NR 101 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 101 4 is more preferred, H, Na, K, Li or NH4 is still more preferred, Na, K or NH4 is still more preferably, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0550] Examples of the compound (β) include an anionic surfactant represented by R 102 -SO3M (wherein R 102 is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may form a ring. M is the same as above). Specifically, those represented by CH3-(CH2) n -SO3M (wherein n is an integer of 2 to 28. M is the same as above) are included.

[0551] From the viewpoint of emulsion stability, the above compound (β) may not contain a carbonyl group (however, excluding the carbonyl group in the carboxy group). Examples of the hydrocarbon-containing surfactant that does not contain the above carbonyl group include, for example, the following formula (B1): R 103 -SO3-M (B1) (In the formula, R 103 is an alkyl group, alkenyl group, alkylene group or alkenylene group containing 6 to 17 carbon atoms, and these may contain an ether bond. M is H, a metal atom, NR 101 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. R 101 is the same or different and is H or an organic group (preferably an organic group not containing fluorine).) Compounds are preferably exemplified. In the above formula (B), R 103 is preferably an alkyl group or an alkenyl group (these may contain an ether group). The alkyl group or alkenyl group in the above R 103 may be linear or branched. The number of carbon atoms in the above R 103 is not limited, but is, for example, 2 to 29.

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

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

[0554] Examples of the above compound (β) include sulfonic acids such as aliphatic, unsaturated aliphatic, and aromatic sulfonic acids, sulfuric acid esters such as aliphatic, unsaturated aliphatic, and aromatic sulfuric acid esters, and salts thereof. Examples of the above sulfonic acids include 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, perfluorobutanesulfonic acid, linear alkylbenzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, DBS, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, butylnaphthalenesulfonic acid. Examples of the above sulfuric acid esters include sodium alkyl sulfate, alpha-sulfo fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, alpha-olefin sulfonate, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid. As the above compound (β), at least one selected from the group consisting of saturated aliphatic and aromatic sulfuric acid esters and salts thereof is particularly preferable, and at least one selected from the group consisting of sodium alkyl sulfate, alpha-sulfo fatty acid ester salt, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, alpha-olefin sulfonate, lauryl sulfate, myristyl sulfate, laureth sulfate, polyoxyethylene alkylphenol sulfonic acid, and salts thereof is more preferable. Examples of the above salt include those in which the hydrogen of the sulfonic acid group is a metal atom of the above formula M, NR 11 4, an optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, but is not particularly limited.

[0555] Examples of the above anionic hydrocarbon surfactant include the following formula (1-0A): [Chemical formula] (In the formula, R 1A ~R 5A is H, a monovalent hydrocarbon group which may contain an ester group between carbon-carbon atoms, or a group represented by the general formula: -X A -A. However, at least one of R 2A and R 5A represents a group represented by the general formula: -X A -A.) X A is, in each occurrence, the same or different, a divalent hydrocarbon group, or a bond; A is, in each occurrence, the same or different, -COOM (where M is H, a metal atom, NR 7 4, an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, and R 7 is H or an organic group (preferably an organic group not containing fluorine)); R 1A ~R 5A Among them, any two of them may be bonded to each other to form a ring. ) Surfactants (1-0A), etc. represented by the formula are also included.

[0556] In the general formula (1-0A), for R 1A ~R 5A , the number of carbon atoms of the monovalent hydrocarbon group which may contain an ester group between carbon-carbon atoms is preferably 1 to 50, and more preferably 5 to 20. Among R 1A ~R 5A , any two of them may be bonded to each other to form a ring. As the above monovalent hydrocarbon group which may contain an ester group between carbon-carbon atoms, an alkyl group is preferable. In the formula, for X A , the number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 50, and more preferably 5 to 20. Examples of the above divalent hydrocarbon group include an alkylene group and an alkanediyl group, and an alkylene group is preferable.

[0557] In the general formula (1-0A), R2A and R 5A Any one of them is preferably a group represented by the general formula: -X A -A, and it is more preferable that R 2A is a group represented by the general formula: -X A -A.

[0558] In the general formula (1-0A), as a preferred embodiment, R 2A is a group represented by the general formula: -X A -A, and R 1A , R 3A , R 4A and R 5A are H. In this case, X A is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0559] In the general formula (1-0A), as another preferred embodiment, R 2A is a group represented by the general formula: -X A -A, and R 1A and R 3A are groups represented by -Y A -R 6 , where Y A is the same or different at each occurrence and is -COO-, -OCO-, or a bond, and R 6 is the same or different at each occurrence and is an alkyl group having 2 or more carbon atoms. In this case, it is preferable that R 4A and R 5A are H.

[0560] Examples of the hydrocarbon surfactant represented by the general formula (1-0A) include glutaric acid or its salt, adipic acid or its salt, pimelic acid or its salt, suberic acid or its salt, azelaic acid or its salt, sebacic acid or its salt, and the like. In addition, the aliphatic carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) may be a two-chain two-hydrophilic group type synthetic surfactant. For example, as a Gemini type surfactant, Gemini SA-F (Chukyo Yushi Co., Ltd.), Gemsurf α142 (dodecyl group with 12 carbon atoms), Gemsurf α102 (with 10 carbon atoms), Gemsurf α182 (with 14 carbon atoms), etc. can be mentioned.

[0561] As the above anionic hydrocarbon surfactant, the following formula I: R-(XZ) n (I) (In the formula, R is a hydrophobic hydrocarbon moiety containing one or more saturated or unsaturated, acyclic or cyclic aliphatic groups. The percentage of the total number of CH3 groups with respect to the total of CH3, CH2 and CH groups in one or more aliphatic groups is at least about 70%, and the hydrophobic moiety does not contain siloxane units. Each X may be the same or different and represents an ionic hydrophilic moiety. Each Z may be the same or different and represents one or more counterions of the ionic hydrophilic moiety. n is 1 to 3.) Compound I represented by this is also included.

[0562] Compound I shows low reactivity with a polymerization initiator and / or a growing fluoropolymer radical in the emulsion polymerization of a fluoromonomer.

[0563] Compound I has the following formula:

Chemical formula

[0564] Compound I has the following formula II:

Chemical formula

[0565] As the compound II, for example, the following compounds are preferred.

Chemical formula

[0566] Compound I is represented by the following formula III:

Chemical formula

[0567] As Compound III, for example, the following compounds are preferable.

Chemical formula

[0568] Even when the above specific hydrocarbon surfactant is not used, the TFE-based polymer composition of the present disclosure is obtained by a production method including a polymerization step of polymerizing only tetrafluoroethylene or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium having a pH of 4.0 or more in the presence of a hydrocarbon surfactant and a polymerization initiator. Conventionally, since a polymerization initiator showing acidity has been used for the polymerization step for producing a TFE-based polymer, the pH of the aqueous medium used in the polymerization was less than 4.0. As a result of intensive studies by the present inventors, it was unexpectedly found that by setting the pH of the aqueous medium used for the polymerization to 4.0 or more, the stability of the polymerization is improved and a TFE-based polymer having a high molecular weight can be produced. The above manufacturing method involves polymerizing only tetrafluoroethylene or tetrafluoroethylene and a modified monomer copolymerizable with tetrafluoroethylene in an aqueous medium having a pH of 4.0 or higher. The pH may be 4.0 or higher, preferably more than 4.0, more preferably 4.5 or higher, still more preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, especially preferably 6.5 or higher, 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 perspective of corrosion of the polymerization tank, it is preferably 12.0 or lower, more preferably 11.5 or lower, and still more preferably 11.0 or lower. The above pH can be measured by a pH meter.

[0569] In the above manufacturing method, the method for adjusting the pH of the aqueous medium to 4.0 or higher is not limited. For example, the pH can be adjusted to 4.0 or higher by using an alkaline aqueous solution, an aqueous dispersion showing alkalinity, or a pH adjuster, but it is not particularly limited. Also, even when using a polymerization initiator that shows acidity when dissolved in an aqueous medium, the pH can be adjusted to 4.0 or higher by further adding an alkali compound such as sodium hydroxide. The above alkali compound may be a compound that dissolves in water and ionizes to produce OH - Any compound that can generate it is acceptable. For example, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc. can be mentioned, but it is not particularly limited. The above polymerization step may include a step of adding an alkali compound to the aqueous medium.

[0570] In the above manufacturing method, the pH of the aqueous medium may be 4.0 or higher throughout all periods of the polymerization step. Also, the pH may be 4.0 or higher in the middle stage of the polymerization step, or the pH may be 4.0 or higher in the latter half of the polymerization step. Further, the pH may be 4.0 or higher in both the middle and latter half of the polymerization step.

[0571] From the start of the polymerization, it is preferable that the pH of the aqueous medium be 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, particularly preferably 99% or more, most preferably 100%) of the period until the polymer solid content concentration reaches 3% by mass (preferably 5% by mass, more preferably 8% by mass, still more preferably 10% by mass, even more preferably 15% by mass, particularly preferably 18% by mass, most preferably 20% by mass, especially preferably 25% by mass). From the point when the polymer solid content concentration reaches 10% by mass (preferably 8% by mass, more preferably 5% by mass, still more preferably 3% by mass, even more preferably at the start of polymerization) to the point when the polymer solid content concentration reaches 15% by mass, it is preferable that the pH of the aqueous medium be 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, particularly preferably 99% or more, most preferably 100%) of the period. From the point when the polymer solid content concentration reaches 15% by mass to the point when the polymer solid content concentration reaches 18% by mass (preferably 20% by mass, more preferably 25% by mass), it is preferable that the pH of the aqueous medium be 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, particularly preferably 99% or more, most preferably 100%) of the period. From the point when the polymer solid content concentration reaches 25% by mass (preferably 20% by mass, more preferably 18% by mass, still more preferably 15% by mass, even more preferably 10% by mass, particularly preferably 8% by mass, most preferably 5% by mass, more preferably 3% by mass, still more preferably at the start of polymerization) to the end point of polymerization, it is preferable that the pH of the aqueous medium be 4.0 or higher for 60% or more (preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, more preferably 99% or more, most preferably 100%) of the period. In any case, the pH of the above aqueous medium is preferably more than 4.0, more preferably 4.5 or more, still more preferably 5.0 or more, even more preferably 5.5 or more, particularly preferably 6.0 or more, especially preferably 6.5 or more, more preferably 7.0 or more, still more preferably 7.5 or more, and even more preferably 8.0 or more.

[0572] In the above production method, the hydrocarbon surfactant is a fluorine-free hydrocarbon surfactant, preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid 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-described other compounds having surfactant properties can be preferably used.

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

[0574] The TFE-based polymer composition of the present disclosure includes a polymerization step of obtaining a TFE-based polymer by polymerizing only tetrafluoroethylene or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant and a polymerization initiator even when the above specific hydrocarbon surfactant is not used, and the hydrocarbon surfactant includes a salt of the hydrocarbon surfactant. In other words, at least a part of the anionic hydrocarbon surfactant in the above polymerization step is in the form of a salt. As a result of intensive studies by the present inventors, unexpectedly, it has been found that an anionic hydrocarbon surfactant can improve the polymerization stability by containing a salt of the anionic hydrocarbon surfactant, and a TFE-based polymer having a large molecular weight can be produced. The anionic hydrocarbon surfactant will be described later. That the anionic hydrocarbon surfactant contains a salt of the hydrocarbon surfactant can be confirmed by measuring the conductivity. In the above production method, it is preferable that the concentration of the salt of the anionic hydrocarbon surfactant in the anionic hydrocarbon surfactant is 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and particularly preferably 95% by mass or more with respect to the total mass of the anionic hydrocarbon surfactant. The ratio of the above salt can be measured by the solution concentration and the conductivity. In the above production method, it is more preferable that the hydrocarbon surfactant is a carboxylic acid type hydrocarbon surfactant. The hydrocarbon surfactant does not contain fluorine. In the salt of the anionic hydrocarbon surfactant, the cation (excluding the hydrogen atom) that replaces the hydrogen atom of the acid is, for example, a metal atom, NR y 4 (R y may be the same or different from each other and is H or an organic group (preferably an organic group not containing fluorine)), an imidazolium that may have a substituent, a pyridinium that may have a substituent, or a phosphonium that may have a substituent. The above R y is preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. As the above cation in the salt of the anionic hydrocarbon surfactant, a metal atom or NR y 4 is preferable, NR y 4 is more preferable, and NH4 is still more preferable. Since the conductivity changes greatly with temperature, a constant temperature bath is used to keep the temperature of the sample solution at 25 °C and the temperature of the cell of the pH meter the same, and then the conductivity is measured.

[0575] In the above production method, it is preferable that the polymerization step is carried out substantially in the absence of the hydrocarbon surfactant in the form of an organic acid. By carrying out the polymerization substantially in the absence of the hydrocarbon surfactant in the form of an organic acid, the stability of the polymerization is further improved, and a high molecular weight TFE-based polymer can be obtained. The phrase "substantially in the absence of the hydrocarbon surfactant in the form of an organic acid" preferably means that the concentration of the organic acid is 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less, and especially preferably 0.01% by mass or less, based on the mass of the obtained aqueous dispersion. In this specification, "organic acid" means an organic compound showing acidity. Examples of the organic acid include carboxylic acids having a -COOH group and sulfonic acids having a -SO3H group, and carboxylic acids are preferred from the viewpoint that it is easy to adjust the pH of an aqueous solution containing the organic acid. Also, the "form of an organic acid" means a form in which the H of the acidic group (for example, -COOH group, -SO3H group, etc.) contained in the organic acid is not free. In the above production method, the hydrocarbon surfactant is an anionic hydrocarbon surfactant.

[0576] In the above polymerization step, the amount of the hydrocarbon surfactant at the start of polymerization is preferably more than 50 ppm with respect to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or more, more preferably 70 ppm or more, still more preferably 80 ppm or more, and even more preferably 100 ppm or more. The upper limit is not particularly limited, but for example, it is preferably 10000 ppm and more preferably 5000 ppm. By the amount of the hydrocarbon surfactant at the start of polymerization being within the above range, an aqueous dispersion with a smaller average primary particle size and better stability can be obtained. Note that the polymerization can be considered to start when the gaseous TFE in the reactor becomes a TFE-based polymer and a pressure drop occurs in the reactor. U.S. Patent No. 3,391,099 (Punderson) discloses a dispersion polymerization of tetrafluoroethylene in an aqueous medium, which consists of two separate stages of a polymerization process: first, the formation of polymer nuclei as nucleation sites, and then a growth stage including the polymerization of established particles. Note that the polymerization usually starts when both the monomer to be polymerized and the polymerization initiator are charged into the reactor. In the present disclosure, an additive related to the formation of nucleation sites is used as a nucleating agent.

[0577] The above polymerization step preferably includes an addition step of adding a composition containing a hydrocarbon-based surfactant after the start of polymerization. By the above addition step, the stability of the polymerization is further improved, and a higher molecular weight TFE-based polymer can be obtained. The above hydrocarbon-based surfactant may be in the form of, for example, a solid (e.g., powder of a hydrocarbon-based surfactant) or a liquid form. The above composition may be any composition containing a hydrocarbon-based surfactant, and may consist only of a hydrocarbon-based surfactant, or may be a solution or dispersion of a hydrocarbon-based surfactant containing a hydrocarbon-based surfactant and a liquid medium. Therefore, the above addition step can also be referred to as a step of adding a hydrocarbon-based surfactant alone or a composition containing a hydrocarbon-based surfactant after the start of polymerization. The hydrocarbon-based surfactant is not limited to one type and may be a mixture of two or more types. The above liquid medium may be either an aqueous medium or an organic solvent, or a combination of an aqueous medium and an organic solvent may be used. Specific examples of the above composition include an aqueous solution in which a hydrocarbon-based surfactant is dissolved in an aqueous medium, an aqueous dispersion in which a hydrocarbon-based surfactant is dispersed in an aqueous medium, and the like.

[0578] In the above addition step, the hydrocarbon surfactant added is preferably in an amount of 0.0001 to 10% by mass based on the aqueous medium. More preferably, it is 0.001% by mass or more based on the aqueous medium, still more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. Also, more preferably, it is 5% by mass or less based on the aqueous medium, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

[0579] Since the stability of polymerization is improved and a higher molecular weight TFE-based polymer can be obtained, the above composition preferably contains a hydrocarbon surfactant and is an aqueous solution having a pH of 5.0 or more. The pH of the above aqueous solution is more preferably 6.0 or more, still more preferably 6.5 or more, even more preferably 7.0 or more, particularly preferably 7.5 or more, and especially preferably 8.0 or more. Also, the upper limit of the pH is not particularly limited and may be 12.0 or less, or may be 11.0 or less.

[0580] The hydrocarbon surfactant in the above addition step is preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid type hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid type hydrocarbon surfactant are not particularly limited. For example, the compound (α) etc. exemplified among the compounds having other surfactant properties described above can be preferably used.

[0581] As the carboxylic acid type hydrocarbon surfactant used in the above polymerization step and addition step, the above surfactant (e), the anionic surfactant represented by the above formula: R 6 (-L-M)2, and the above formula: R 7Among the anionic surfactants represented by (-L-M)3, those having a carboxy group (-COOH) or a group in which a hydrogen atom of the carboxy group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.), the above compound (α), the above surfactant (1-0A), and at least one selected from the group consisting of those obtained by subjecting these surfactants to radical treatment or oxidation treatment are preferred. The above carboxylic acid type hydrocarbon surfactant may be used alone or as a mixture of two or more. In the above compound (α), the above-described formula: R 102 -COOM (wherein R 102 and M are the same as above).) includes not only an anionic hydrocarbon surfactant (preferably, a compound represented by the formula (A1)) represented by the above formula, but also an anionic surfactant represented by the above-described formula: R-L-M (wherein R, L, and M are the same as above), and among the above surfactants (c) and (d), those having a carboxy group (-COOH) or a group in which a hydrogen atom of the carboxy group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.).

[0582] The above carboxylic acid type hydrocarbon surfactant is preferably the above compound (α), and more preferably at least one selected from the group consisting of the compound represented by the above formula (A1), the compound in which A c is -COOX c in the above formula (c), the compound in which A d is -COOX d in the above formula (d), the compound in which A e is -COOM e in the above formula (e), the compound in which A is -COOM in the above formula (1-0A), and those obtained by subjecting these compounds to radical treatment or oxidation treatment. Even more preferably, at least one selected from the group consisting of the compound represented by the above formula (A1) and those obtained by subjecting the compound to radical treatment or oxidation treatment is preferred. In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof, and those obtained by subjecting these compounds to radical treatment or oxidation treatment is preferable. As the above salts, hydrogen of the carboxy group is a metal atom of the above-described formula M, 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, and is not particularly limited.

[0583] The above production method preferably polymerizes tetrafluoroethylene in the substantial absence of a fluorine-containing surfactant. In the above production method, "in the substantial absence of a fluorine-containing surfactant" means that the fluorine-containing surfactant is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, still more preferably 10 mass ppb or less, still more preferably less than 10 mass ppb, still more preferably 1 mass ppb or less, and particularly preferably less than 1 mass ppb with respect to the aqueous medium. "In the substantial absence of a fluorine-containing surfactant" also means that there is no intentional addition of a fluorine-containing surfactant.

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

[0585] The above fluorine-containing surfactant may also be a surfactant containing fluorine having a molecular weight of the anionic portion of 1000 or less, preferably 800 or less. Note that the above "anionic portion" means the portion excluding the cation of the above fluorine-containing surfactant. For example, in the case of F(CF2) n1 COOM represented by the following formula (I), it is the portion of "F(CF2) n1 COO".

[0586] Specific examples of the fluorosurfactant include those described in US Patent Application Publication No. 2007 / 0015864, US Patent Application Publication No. 2007 / 0015865, US Patent Application Publication No. 2007 / 0015866, US Patent Application Publication No. 2007 / 0276103, US Patent Application Publication No. 2007 / 0117914, US Patent Application Publication No. 2007 / 142541, US Patent Application Publication No. 2008 / 0015319, US Patent No. 3250808, US Patent No. 3271341, Japanese Patent Application Laid-Open No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, International Publication No. 2007 / 119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, US Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, International Publication No. 2013 / 189826, and the like.

[0587] Examples of the anionic fluorosurfactant include compounds represented by the above general formula (N 0 ).

[0588] As described above, examples of the anionic fluorosurfactant include carboxylic acid-based fluorosurfactants, sulfonic acid-based fluorosurfactants, and the like.

[0589] The TFE-based polymer composition of the present disclosure can be preferably produced by a production method including an addition step of adding at least one selected from the group consisting of a radical scavenger and a decomposer of a polymerization initiator. The addition step is performed during the step of performing the above-described emulsion polymerization in an aqueous medium. By adding a radical scavenger or a decomposer of a polymerization initiator, the radical concentration during polymerization can be adjusted. From the viewpoint of reducing the radical concentration, a radical scavenger is preferred.

[0590] As the radical scavenger, a compound that does not have a restart ability after adding to or undergoing chain transfer with free radicals in the polymerization system is used. Specifically, a compound that easily undergoes a chain transfer reaction with primary radicals or growing radicals and then generates stable radicals that do not react with monomers, or a compound that has a function of easily undergoing an addition reaction with primary radicals or growing radicals to generate stable radicals is used. What is generally called a chain transfer agent is characterized by its activity in terms of a chain transfer constant and a restart efficiency. Among chain transfer agents, those with a restart efficiency of almost 0% are called radical scavengers. The above radical scavenger can also be, for example, a compound in which the chain transfer constant with TFE at the polymerization temperature is larger than the polymerization rate constant and the restart efficiency is substantially 0%. "The restart efficiency is substantially 0%" means that the generated radicals are converted into stable radicals by the radical scavenger. Preferably, it is a compound in which the chain transfer constant (Cs) with TFE at the polymerization temperature (= chain transfer rate constant (kc) / polymerization rate constant (kp)) is greater than 0.1. For the above compound, it is more preferable that the chain transfer constant (Cs) is 0.5 or more, still more preferable that it is 1.0 or more, even more preferable that it is 5.0 or more, and particularly preferable that it is 10 or more.

[0591] As the radical scavenger in the present disclosure, for example, at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N - diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl2) is preferable. Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m - or p - salicylic acid, gallic acid, naphthol, etc. Examples of the above unsubstituted phenol include о -, m - or p - nitrophenol, о -, m - or p - aminophenol, p - nitrosophenol, etc. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, naphthoresorcinol, etc. Examples of the aromatic amines include o-, m- or p-phenylenediamine, benzidine and the like. Examples of the quinone compounds include o-, m- or p-benzoquinone, 1,4-naphthoquinone, alizarin and the like. Examples of the thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN) and the like. Among the above radical scavengers, aromatic hydroxy compounds are preferred, unsubstituted phenols or polyhydric phenols are more preferred, and hydroquinone is even more preferred.

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

[0593] The decomposer of the polymerization initiator may be any compound that can decompose 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 the sulfites include sodium sulfite and ammonium sulfite. Examples of the copper salts include copper(II) sulfate, and examples of the iron salts include iron(II) sulfate. The addition amount of the decomposer of the above polymerization initiator is added in the range of 25 to 300% by mass with respect to the amount of the oxidizing agent combined as the polymerization initiator (the redox initiator described later). Preferably it is 25 to 150% by mass, and more preferably 50 to 100% by mass. From the perspective of reducing the standard specific gravity, the addition amount of the decomposer of the polymerization initiator is preferably an amount corresponding to 3 to 500% (molar basis) of the polymerization initiator concentration. A more preferable lower limit is 5% (molar basis), still more preferably 8% (molar basis), still more preferably 10% (molar basis), still more preferably 13% (molar basis), and even more preferably 15% (molar basis). A more preferable upper limit is 400% (molar basis), still more preferably 300% (molar basis), even more preferably 200% (molar basis), and particularly preferably 100% (molar basis).

[0594] At least one selected from the group consisting of a radical scavenger and a decomposer of a polymerization initiator is preferably added when the concentration of the TFE-based polymer formed in the aqueous medium is 5% by mass or more. More preferably, it is when it is 10% by mass or more. Also, it is preferably added when the concentration of the TFE-based polymer formed in the aqueous medium is 40% by mass or less. More preferably, it is when it is 35% by mass or less, and still more preferably, it is when it is 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 not all at once, but over time, continuously or in portions.

[0596] The polymerization step may be one in which tetrafluoroethylene is polymerized in the presence of a nucleating agent.

[0597] As the nucleating agent, for example, it is preferably at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents. In this case, the polymerization step is preferably a step of obtaining a TFE-based polymer by polymerizing tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon-based surfactant and the nucleating agent.

[0598] As the fluoropolyether, perfluoropolyether is preferable.

[0599] The fluoropolyether preferably has repeating units represented by formulae (1a) to (1d). (-CFCF3-CF2-O-) n (1a) (-CF2-CF2-CF2-O-) n (1b) (-CF2-CF2-O-) n -(-CF2-O-) m (1c) (-CF2-CFCF3-O-) n -(-CF2-O-) m (1d) (In formulae (1a) to (1d), m and n are integers of 1 or more.)

[0600] As the fluoropolyether, a fluoropolyether acid or a salt thereof is preferable, 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 acid or a salt thereof, a salt of the fluoropolyether acid is preferable, an ammonium salt of the fluoropolyether acid is more preferable, and an ammonium salt of the fluoropolyether carboxylic acid is still more preferable.

[0601] The fluoropolyether acid or a salt thereof can have any chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Two or more types of fluorocarbon groups can be present in the molecule.

[0602] As the fluoropolyether acid or a salt thereof, the following formula: CF3-CF2-CF2-O(-CFCF3-CF2-O-) n CFCF3-COOH, CF3-CF2-CF2-O(-CF2-CF2-CF2-O-) n -CF2-CF2COOH, or, HOOC-CF2-O(-CF2-CF2-O-) n -(-CF2-O-) m CF2COOH (wherein m and n are the same as defined above.) It is preferable that the compound is represented by the formula or a salt thereof.

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

[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. 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 production of a single specific fluoropolyether compound, the fluoropolyether can contain multiple compounds in various proportions within the molecular weight range relative to the number average molecular weight.

[0605] The above fluoropolyether preferably has a number average molecular weight of 800 g / mol or more. Since the fluoropolyether acid or its salt may be difficult to disperse in an aqueous medium, it preferably has a number average molecular weight of 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 above fluoropolyether is preferably 5 to 3000 ppm with respect to the aqueous medium, more preferably 5 to 2000 ppm, and the even more preferred lower limit is 10 ppm and the even more preferred upper limit is 100 ppm.

[0607] Examples of the nonionic surfactant as the above nucleating agent include the nonionic surfactants described above, and it is preferably a nonionic surfactant th...

Claims

1. A tetrafluoroethylene-based polymer composition for use in a binder for electrochemical devices, the polymer composition having a carboxyl group number of 10 carbon atoms in the main chain. 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. 3. The tetrafluoroethylene polymer composition according to claim 1, having a standard specific gravity of 2.130 or more and 2.180 or less.

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

5. A binder for electrochemical devices consisting essentially of a tetrafluoroethylene-based polymer composition, the tetrafluoroethylene-based polymer composition having a carboxyl group number of 10 or more and a main chain carbon number of 10 or more. 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. 7. The binder for electrochemical devices according to claim 5, wherein the tetrafluoroethylene polymer composition has an endothermic peak temperature of 333° C. or higher and 350° C. or lower.

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

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

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

11. 7. The binder for electrochemical devices according to claim 5 or 6, which is a binder for lithium ion secondary batteries and is in the form of a powder.

12. 7. An electrode mixture comprising the tetrafluoroethylene polymer composition according to claim 1 or 2, or the binder for electrochemical devices according to claim 5 or 6, and an electrode active material.

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

14. 7. An electrode comprising the tetrafluoroethylene polymer composition according to claim 1 or 2, or the binder for electrochemical devices according to claim 5 or 6, an electrode active material, and a current collector.

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

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