Fluoropolymers, aqueous solutions, coating compositions, and methods for producing fluoropolymers

Abstract

Provided is a fluoropolymer containing a polymerization unit (I) based on a monomer (I) represented by general formula (I) and a polymerization unit (II) based on a monomer (II) represented by formula (II).　Formula (I): CX1X3=CX2R(-CZ1Z2-A0)m (In the formula, each of X1 and X3 independently represents F, Cl, H, or CF3; X2 represents H, F, an alkyl group, or a fluorine-containing alkyl group; A0 represents an anionic group; R represents a linking group; each of Z1 and Z2 independently represents H, F, an alkyl group, or a fluorine-containing alkyl group; and m represents an integer of 1 or larger.)　Formula (II): CHF=CHF

Description

Technical Field

[0001] The present disclosure relates to fluoropolymers, aqueous solutions, coating compositions, and methods for producing fluoropolymers.

Background Art

[0002] Patent Document 1 describes a composition comprising water and a water-soluble polymer in which the proportion of hydrogen atoms bonded to carbon atoms substituted with fluorine atoms is 50% or more, and the content of a compound having a molecular weight of 700 or more and 3000 or less is 3.5% or less with respect to the water-soluble polymer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a fluoropolymer having a high decomposition start temperature, being rapidly decomposed at a temperature equal to or higher than the decomposition start temperature, and having excellent water solubility.

Means for Solving the Problems

[0005] According to the present disclosure, a fluoropolymer containing a polymerization unit (I) based on a monomer (I) represented by the general formula (I) and a polymerization unit (II) based on a monomer (II) represented by the formula (II) is provided. CX , 1 , , 0 ,

[0005] , 1 , 3 , 3 , , m , 2 , , 2 , , 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; X2 is H, F, alkyl group or fluorine-containing alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 Each of these is independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more. CHF=CHF (II)

[0006] In the fluoropolymer of this disclosure, it is preferable that the content of polymerization unit (I) is 20 to 99 mol% of the total polymerization units constituting the fluoropolymer, and the content of polymerization unit (II) is 80 to 1 mol% of the total polymerization units constituting the fluoropolymer. In the fluoropolymer of this disclosure, it is more preferable that the content of polymerization unit (I) is 40 to 99 mol% relative to the total polymerization units constituting the fluoropolymer, and the content of polymerization unit (II) is 60 to 1 mol% relative to the total polymerization units constituting the fluoropolymer. In the fluoropolymer of this disclosure, it is preferable that the content of monomer (I) dimers and trimers is 1.0% by mass or less relative to the fluoropolymer. In the fluoropolymer of this disclosure, it is preferable that the content of dimers and trimers composed of monomer (I) and monomer (II) is 1.0% by mass or less relative to the fluoropolymer. In the fluoropolymers disclosed herein, A 0 However, -SO3M or -COOM(M is H, a metal atom, NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (It is preferably H or an organic group.) In the fluoropolymer of this disclosure, it is preferable that the polymerization unit (I) is at least one selected from the group consisting of polymerization unit (1) based on monomer (1) represented by general formula (1) and polymerization unit (2) based on monomer (2) represented by general formula (2). CX2 = CY(-CZ2-O-Rf-A) (1) (In the formula, X is the same or different H or F, Y is H, F, an alkyl group or a fluorinated alkyl group, and Z is the same or different H, F, an alkyl group or a fluoroalkyl group. Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond. A is -COOM, -SO3M, -OSO3M or -C(CF3)2OM (M is H, a metal atom, NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (wherein X, Y, and Z are H or organic groups, at least one of them contains a fluorine atom.) CX2 = CY(-O-Rf-A) (2) (In the formula, X is either H or F, either the same or different; Y is H, F, an alkyl group, or a fluorinated alkyl group; Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and possessing an ether linkage or a keto group. A is the same as described above.) In the fluoropolymers disclosed herein, A is -SO3M or -COOM(M is H, a metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (It is preferably H or an organic group.) The fluoropolymer disclosed herein has a weight-average molecular weight (Mw) of 1.0 × 10⁻⁶. 4 It is preferable that the above conditions are met. The fluoropolymers of this disclosure preferably have a molecular weight distribution (Mw / Mn) of 3.0 or less. The fluoropolymer of this disclosure preferably has an ion exchange capacity of 0.8 meq / g or more. The fluoropolymer of this disclosure preferably has an ion exchange rate (IXR) of 43 or less.

[0007] Furthermore, this disclosure provides an aqueous solution containing the above-mentioned fluoropolymer.

[0008] The aqueous solution of the present disclosure preferably contains 1.0% by mass or more of the fluoropolymer relative to the aqueous solution.

[0009] Furthermore, this disclosure provides a coating composition containing the above-mentioned fluoropolymer or the above-mentioned aqueous solution.

[0010] Furthermore, according to this disclosure, a method for producing the above-mentioned fluoropolymer is provided, which involves polymerizing monomer (I) and monomer (II) to obtain the fluoropolymer.

[0011] In the manufacturing method of this disclosure, it is preferable that the polymerization temperature is 70°C or lower. In the manufacturing method of this disclosure, it is preferable to carry out the polymerization in an aqueous medium. In the manufacturing method of this disclosure, the polymerization is carried out in the presence of a polymerization initiator, and it is preferable that the polymerization initiator is a persulfate. In the manufacturing method of the present disclosure, the polymerization is carried out in an aqueous medium in the presence of a polymerization initiator, and it is preferable that the total amount of the polymerization initiator used in the polymerization is 0.00001 to 10% by mass relative to the aqueous medium. In the manufacturing method of the present disclosure, it is preferable to carry out the polymerization in an aqueous medium, recover the aqueous medium and the composition containing the fluoropolymer after the polymerization is completed, and treat the composition by at least one means selected from the group consisting of ultrafiltration, microfiltration, dialysis membrane treatment, liquid-liquid separation and reprecipitation. [Effects of the Invention]

[0012] According to this disclosure, it is possible to provide a fluoropolymer that has a high decomposition initiation temperature, decomposes rapidly above the decomposition initiation temperature, and exhibits excellent water solubility. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 shows a curve representing the change in heater temperature over time during the TG-DTA analysis performed in Example 1, and a graph showing the TG curve obtained from the TG-DTA analysis. [Modes for carrying out the invention]

[0014] Before describing this disclosure in detail, we define or explain some of the terms used in this disclosure.

[0015] In this disclosure, "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. Examples of such "organic groups" are: Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2-, and RaNRbSO2- (In these formulas, Ra is independent of, Alkyl molecules which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, Rb is independently an alkyl group which may have H or one or more substituents. It includes. The above organic group is preferably an alkyl group which may have one or more substituents.

[0016] Furthermore, in this disclosure, “substituent” means a substituteable group. Examples of such “substituent” are aliphatic group, aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino This includes groups, aromatic amino groups, heterocyclic amino groups, aliphatic oxycarbonylamino groups, aromatic oxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxyl groups, cyano groups, sulfo groups, carboxyl groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, and diaromatic oxyphosphinyl groups.

[0017] The above aliphatic group may be saturated or unsaturated, and may also include a hydroxyl group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic group include alkyl groups having a total of 1 to 8 carbon atoms, preferably 1 to 4, such as a methyl group, ethyl group, vinyl group, cyclohexyl group, carbamoylmethyl group, etc.

[0018] The above aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. Examples of the above aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

[0019] The above heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. Examples of the above heterocyclic group include a 5-6 membered heterocycle with a total of 2 to 12 carbon atoms, preferably 2 to 10, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.

[0020] The above acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. Examples of the above acyl group include acyl groups with a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

[0021] The above acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the above acylamino group include an acylamino group having a total of 2 to 12 carbon atoms, preferably 2 to 8, and an alkylcarbonylamino group having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, and a propanoylamino group.

[0022] The above aliphatic oxycarbonyl group may be saturated or unsaturated, and may also have a hydroxyl group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic oxycarbonyl group include alkoxycarbonyl groups having a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, and (t)-butoxycarbonyl group.

[0023] The above carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, or an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, or an N-phenylcarbamoyl group.

[0024] The above aliphatic sulfonyl group may be saturated or unsaturated, and may also have a hydroxyl group, aromatic group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic sulfonyl group include alkyl sulfonyl groups having a total of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methanesulfonyl group.

[0025] The above aromatic sulfonyl group may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. Examples of the above aromatic sulfonyl group include aryl sulfonyl groups with a total of 6 to 10 carbon atoms, such as a benzenesulfonyl group.

[0026] The above amino group may also have an aliphatic group, an aromatic group, a heterocyclic group, etc.

[0027] The above acylamino group may include, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, or a propanoylamino group. Examples of the above acylamino group include an acylamino group having a total of 2 to 12 carbon atoms, preferably an acylamino group having a total of 2 to 8 carbon atoms, more preferably an alkylcarbonylamino group having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, or a propanoylamino group.

[0028] The above-mentioned aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, or a 2-pyridinesulfonamide group.

[0029] The above-mentioned sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above-mentioned sulfamoyl group include a sulfamoyl group, an alkyl sulfamoyl group having a total of 1 to 9 carbon atoms, a dialkyl sulfamoyl group having a total of 2 to 10 carbon atoms, an aryl sulfamoyl group having a total of 7 to 13 carbon atoms, a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkyl sulfamoyl group having a total of 1 to 7 carbon atoms, a dialkyl sulfamoyl group having a total of 3 to 6 carbon atoms, an aryl sulfamoyl group having a total of 6 to 11 carbon atoms, a heterocyclic sulfamoyl group having a total of 2 to 10 carbon atoms, for example, a sulfamoyl group, a methyl sulfamoyl group, an N,N-dimethyl sulfamoyl group, a phenyl sulfamoyl group, a 4-pyridine sulfamoyl group, etc.

[0030] The above aliphatic oxy group may be saturated or unsaturated, and may also include a methoxy group, ethoxy group, i-propyloxy group, cyclohexyloxy group, methoxyethoxy group, etc. Examples of the above aliphatic oxy group include alkoxy groups having a total of 1 to 8 carbon atoms, preferably 1 to 6, such as a methoxy group, ethoxy group, i-propyloxy group, cyclohexyloxy group, methoxyethoxy group, etc.

[0031] The above aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused with the aryl group, an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 total carbon atoms, an aliphatic oxy group having 1 to 4 total carbon atoms, a halogen atom, a carbamoyl group having 1 to 4 total carbon atoms, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 total carbon atoms.

[0032] The above aliphatic thio group may be saturated or unsaturated, and more preferably an alkyl thio group having a total of 1 to 8 carbon atoms, or more preferably 1 to 6 carbon atoms, such as a methyl thio group, an ethyl thio group, a carbamoyl methyl thio group, or a t-butyl thio group.

[0033] The above-mentioned carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the above-mentioned carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 9 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 10 carbon atoms, an arylcarbamoylamino group having a total of 7 to 13 carbon atoms, a heterocyclic carbamoylamino group having a total of 3 to 12 carbon atoms, preferably a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 7 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 6 carbon atoms, an arylcarbamoylamino group having a total of 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 10 carbon atoms. For example, the above-mentioned carbamoylamino group, methylcarbamoylamino group, N,N-dimethylcarbamoylamino group, phenylcarbamoylamino group, 4-pyridinecarbamoylamino group, etc.

[0034] In this disclosure, the ranges represented by endpoints include all numerical values ​​that fall within that range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0035] In this disclosure, the phrase "at least 1" includes all numbers greater than or equal to 1 (for example, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0036] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.

[0037] (Fluoropolymer) The fluoropolymers of this disclosure contain polymerization units (I) and polymerization units (II). Because the fluoropolymers of this disclosure contain polymerization units (I) and polymerization units (II), they have a high decomposition onset temperature and decompose rapidly when heated above the decomposition onset temperature. Therefore, a coating film containing the fluoropolymers of this disclosure can stably coat an article up to a certain temperature and can be easily removed by heating above the decomposition onset temperature. Furthermore, because the fluoropolymers of this disclosure have high water solubility, high-concentration aqueous solutions for coating can be easily prepared by using the fluoropolymers of this disclosure.

[0038] A polymerization unit (I) is a polymerization unit based on monomer (I) represented by 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 These are, independently, F, Cl, H, or CF3; X 2 is H, F, alkyl group or fluorine-containing alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 Each of these is independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more.

[0039] Furthermore, polymerization unit (II) is a polymerization unit based on monomer (II) represented by formula (II). CHF=CHF (II)

[0040] In this disclosure, the anionic group includes not only anionic groups such as sulfate groups and carboxylate groups, but also functional groups that give anionic groups such as acidic groups like -COOH and acid-base groups like -COONH4. Anionic groups include sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, or -C(CF3)2OM (wherein M is -H, a metal atom, -NR). 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (where is H or an organic group.) is preferred.

[0041] The fluoropolymers of this disclosure may contain one or more monomers as monomer (I) represented by general formula (I).

[0042] R is a linking group. In this disclosure, “linking group” is an (m+1) valence linking group, and if m is 1, it is a divalence linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. There is no upper limit, but for example, it may be 100 or less, or 50 or less.

[0043] 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 esters, amides, sulfonamides, carbonyls, carbonates, urethanes, ureas, and carbamates. The above linking group may not contain carbon atoms and may contain catenary heteroatoms such as oxygen, sulfur, or nitrogen.

[0044] m is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1. If m is an integer greater than or equal to 2, then Z 1 , Z 2 and A 0 They may be the same or different. Next, we will describe a preferred configuration when m is 1 in general formula (I).

[0045] R is preferably a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0046] When R is a divalent organic group, the hydrogen atom bonded to the carbon atom may be replaced by a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. Furthermore, R may be linear or branched, and may be cyclic or acyclic. In addition, R may contain a functional group (for example, an ester, ether, ketone (keto group), amine, halide, etc.).

[0047] R may also be a non-fluorinated divalent organic group, or a partially fluorinated or perfluorinated divalent organic group.

[0048] R may be, for example, a hydrocarbon group in which no fluorine atoms are bonded to a carbon atom, a hydrocarbon group in which some of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms, or a hydrocarbon group in which all of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms. These may contain oxygen atoms, double bonds, or functional groups.

[0049] R is preferably a hydrocarbon group having 1 to 100 carbon atoms, which may contain an ether bond or a keto group, and the hydrocarbon group may have some or all of the hydrogen atoms bonded to the carbon atoms substituted with fluorine.

[0050] R is preferably -(CH2) a -,-(CF2) a -,-(CF2) a -O-, -O-(CF2) a -,-(CF2) a -O-(CF2) b -, -O(CF2) a -O-(CF2) b -,-(CF2) a -[O-(CF2) b ] c -, -O(CF2) a -[O-(CF2) b ] c -,-[(CF2) a -O] b -[(CF2) c -O] d -, -O[(CF2) a -O] b -, -O[(CF2) a -O] b -[(CF2) c -O] d -,-O-[CF2CF(CF3)O] a -(CF2) b -, -O-(CF2) a -O-[CF(CF3)CF2O] b -O-, -O-[CF2CF(CF3)O] a -(CF2) b -O-, -O-[CF2CF(CF3)O] a-(CF2) b -O-[CF(CF3)CF2O] c -O-、-[CF2CF(CF3)O] a -、-[CF(CF3)CF2O] a -、-(CF2) a -O-[CF(CF3)CF2O] a -、-(CF2) a -O-[CF(CF3)CF2O] a -(CF2) b -、-[CF2CF(CF3)] a -CO-(CF2) b -、および、これらの組み合わせから選択される少なくとも1種である。 Where a, b, c, and d are each independently at least 1 or more. a, b, c, and d may independently be 2 or more, 3 or more, 4 or more, 10 or more, 20 or more. The upper limit of a, b, c, and d is, for example, 100.

[0051] As R, the general formula (r1): -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g - (r1) (Where X 6 is each independently H, F, or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, and g is 0 or 1) is preferably a divalent group represented by, and the general formula (r2): -CF2-O-(CX 7 2) e -(O) g - (r2) (Where X 7 is each independently H, F, or CF3, e is an integer from 0 to 3, and g is 0 or 1) is a more preferred divalent group represented by.

[0052] Specific examples suitable as R include -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -O-CF2-, -O-CF2CF2-, -O-CF2CF2CF2-, -O-CF2CF2CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CH2-, etc. Among them, R is preferably a perfluoroalkylene group which may contain an oxygen atom. Specifically, -CF2-O-, -CF2-O-CF2-, -O-CF2-, -O-CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, or -CF2-O-CF(CF3)CF2-O- is preferred.

[0053] -R-CZ in general formula (I) 1 Z 2 - As, general formula (s1): -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 - (s1) (In the formula, X 6 are each independently H, F or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, and Z 1 and Z 2 are each independently H, F, an alkyl group or a fluorinated alkyl group), and in formula (s1), Z 1 and Z 2 are more preferably F or CF3, and it is even more preferable that one is F and the other is CF3.

[0054] Furthermore, in general formula (I), -R-CZ 1 Z 2 -For example, the general formula (s2): -CF2-O-(CX 7 2) e -(O) g -CZ 1 Z 2 - (s2) (In the formula, X 7 Each of them is independently H, F, or CF3, e is an integer from 0 to 3, g is 0 or 1, and Z 1 and Z 2 Preferably, each of these is independently represented as H, F, an alkyl group, or a fluorine-containing alkyl group, and in formula (s2), Z 1 and Z 2 F or CF3 is more preferable, and it is even more preferable that one is F and the other is CF3.

[0055] General formula (I) -R-CZ 1 Z 2Examples include -CF2-O-CF2-, -O-CF2CF2-, -O-CF2CF2CF2-, -O-CF2CF2CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF2CF2-, -O-CF2CF(CF3)-O-CF2CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-C(CF3)2-, -CF2-O-CF2-CF2-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2-C(CF3)2-, -CF2-O-CF2CF2-CF2-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF2CF2-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)CF2-CF2-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-C(CF3)2-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, or -CF2-O-CF(CF3)CF2-O-C(CF3)2-. Among them, -O-CF2CF2-, -O-CF2CF2CF2-, -O-CF2CF2CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)CF2-CF(CF3)-, or -CF2-O-CF(CF3)CF2-O-CF(CF3)- are more preferred, and -O-CF2CF2-, -O-CF2CF(CF3)-O-CF2CF2- are even more preferred.

[0056] Anionic group (A 0) may be -SO2M, -SO3M, -OSO3M, -COOM, -SO2NR'CH2COOM, -CH2OP(O)(OM)2, [-CH2O]2P(O)(OM), -CH2CH2OP(O)(OM)2, [-CH2CH2O]2P(O)(OM), -CH2CH2OSO3M, -P(O)(OM)2, -SO2NR'CH2CH2OP(O)(OM)2, [-SO2NR'CH2CH2O]2P(O)(OM), -CH2OSO3M, -SO2NR'CH2CH2OSO3M, or -C(CF3)2OM. Among these, -SO3M, -OSO3M, -COOM, -P(O)(OM)2 or -C(CF3)2OM are preferred, -COOM, -SO3M, -OSO3M, -P(O)(OM)2 or -C(CF3)2OM are more preferred, -SO3M, -COOM or -P(O)(OM)2 are even more preferred, and -SO3M or -COOM are particularly preferred.

[0057] M is H, a metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 is either H or an organic group.

[0058] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0059] For M, this could be -H, a metal atom, or NR. 7 4 is preferred, and -H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 4 is more preferred, -H, -Na, -K, -Li or NH4 is even more preferred, -H, -Na, -K or NH4 is even more preferred, and -H, -Na or NH4 is particularly preferred.

[0060] In a fluoropolymer, each polymerization unit (I) may have different anionic groups, or it may have the same anionic group.

[0061] The monomer (I) is also preferably the monomer represented by general formula (Ia). The fluoropolymer is also preferably a polymer that contains polymerization units (Ia) based on monomers represented by general formula (Ia). CF2 = CF - O - Rf 0 -A 0 (Ia) (In the formula, A 0 Rf is an anionic group, 0 This is a perfluorinated divalent linking group that is perfluorinated and may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0062] The monomer (I) is also preferably the monomer represented by general formula (Ib). The fluoropolymer is also preferably a polymer containing polymerization units (Ib) based on monomers represented by general formula (Ib). CH2=CH-O-Rf 0 -A 0 (Ib) (In the formula, A 0 Rf is an anionic group, 0 (This is a perfluorinated divalent linking group defined by formula Ia.)

[0063] In general formula (I), A 0 A is a sulfate group, which is one preferred form. 0 For example, -CH2OSO3M, -CH2CH2OSO3M, or -SO2NR'CH2CH2OSO3M, where R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0064] A 0When is a sulfate group, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2CH2OSO3M), CF2=CF(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF(CF3)CH2OSO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M), CH2=CH(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(OCF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(OCF2CF2CF2CH2OSO3M), etc. In the above formula, M is the same as above.

[0065] In general formula (I), A 0 A sulfonate group is also a preferred form. 0 For example, this is -SO3M, where M is the same as above.

[0066] A 0 When is a sulfonate group, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2SO3M), CF2=CF(O(CF2)3SO3M), CF2=CF(O(CF2)4SO3M), CF2=CF(OCF2CF(CF3)SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M), CH2=CH(OCF2CF2SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M), CH2=CH(O(CF2)4SO3M), CH2=CH(O(CF2)3SO3M), etc. In the above formula, M is the same as above.

[0067] In general formula (I), A 0 A carboxylate group is also a preferred form. 0 For example, COOM or SO2NR'CH2COOM, where R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above. 0When is a carboxylate group, the monomers represented by general formula (I) are CF2=CF(OCF2CF2COOM), CF2=CF(O(CF2)3COOM), CF2=CF(O(CF2)4COOM), CF2=CF(O(CF2)5COOM), CF2=CF(OCF2CF(CF3)COOM), and CF2=CF(OCF2CF(CF3)O(CF2) n Examples include COOM) (where n is greater than 1), CH2=CH(OCF2CF2COOM), CH2=CH(O(CF2)4COOM), CH2=CH(O(CF2)3COOM), CF2=CF(OCF2CF2SO2NR'CH2COOM), CF2=CF(O(CF2)4SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR'CH2COOM), CH2=CH(OCF2CF2SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR'CH2COOM), CH2=CH(O(CF2)4SO2NR'CH2COOM), CH2=CH(O(CF2)3SO2NR'CH2COOM), etc. In the above formula, R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0068] In general formula (I), A 0 A phosphate group is also a preferred form. 0 Examples include -CH2OP(O)(OM)2, [-CH2O]2P(O)(OM), -CH2CH2OP(O)(OM)2, [-CH2CH2O]2P(O)(OM), [-SO2NR'CH2CH2O]2P(O)(OM), or SO2NR'CH2CH2OP(O)(OM)2, where R' is an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0069] A 0When is a phosphate, the monomers represented by general formula (I) are CF2=CF(OCF2CF2CH2OP(O)(OM)2), CF2=CF(O(CF2)4CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2), CF2=CF(OC Examples include F2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CH2=CH(OCF2CF2CH2OP(O)(OM)2), CH2=CH(O(CF2)4CH2OP(O)(OM)2), CH2=CH(O(CF2)3CH2OP(O)(OM)2), etc. In the above formulas, M is the same as above.

[0070] In general formula (I), A 0 A phosphonate group is also a preferred form. 0 When is a phosphonate group, the monomers represented by general formula (I) include CF2=CF(OCF2CF2P(O)(OM)2), CF2=CF(O(CF2)4P(O)(OM)2), CF2=CF(OCF2CF(CF3)P(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2), CH2=CH(OCF2CF2P(O)(OM)2), CH2=CH(O(CF2)4P(O)(OM)2), and CH2=CH(O(CF2)3P(O)(OM)2), where M is the same as above.

[0071] The monomer (I) is preferably monomer (1) represented by general formula (1). The fluoropolymer is preferably a fluoropolymer (1) that includes a polymerization unit (I) based on a monomer (1) represented by general formula (1) as the polymerization unit (I). CX2 = CY(-CZ2-O-Rf-A) (1) (In the formula, X is the same or different H or F, Y is H, F, an alkyl group or a fluorinated alkyl group, and Z is the same or different H, F, an alkyl group or a fluoroalkyl group. Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond. A is -COOM, -SO3M, -OSO3M or -C(CF3)2OM (M is H, a metal atom, NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (wherein X, Y, and Z are H or organic groups, at least one of them contains a fluorine atom.)

[0072] The above-mentioned fluorine-containing alkylene groups having ether bonds with 2 to 100 carbon atoms do not include structures where the oxygen atom is at the terminal end, and are alkylene groups that contain ether bonds between carbon atoms.

[0073] In general formula (1), X is either H or F. X may be both F, or at least one of them may be H. For example, one may be F and the other H, or both may be H.

[0074] In general formula (1), Y is H, F, an alkyl group, or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have 1 or more carbon atoms. The alkyl group may have 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. 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 fluorine-containing alkyl group may have 6 or fewer carbon atoms, more preferably 4 or fewer, and even more preferably 3 or fewer. As Y, H, F, or CF3 are preferred, and F is more preferred.

[0075] In general formula (1), Z is either the same or different H, F, an alkyl group, or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. As Z, H, F, or CF3 are preferred, and F is more preferred.

[0076] In general formula (1), at least one of X, Y, and Z contains a fluorine atom. For example, X may be H and Y and Z may be F.

[0077] In general formula (1), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.

[0078] The number of carbon atoms in the above-mentioned fluorine-containing alkylene group is preferably 2 or more. Furthermore, the number of carbon atoms in the above-mentioned fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. Examples of the above-mentioned fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CF2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The above-mentioned fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0079] The number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 3 or more. Furthermore, the number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorinated alkylene group having the ether bond described above is, for example, a general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 H or F;Z respectively 4 It is also preferable that is a divalent base represented by H, F, or CF3; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0080] Specifically, the above fluorine-containing alkylene groups having an ether bond include -CF2CF(CF3)OCF2-, -CF(CF3)CF2-O-CF(CF3)-, and -(CF(CF3)CF2-O) n -CF(CF3)- (where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having the above ether bond is preferably a perfluoroalkylene group.

[0081] In general formula (1), A is -COOM, -SO3M, -OSO3M, or -C(CF3)2OM (where M is H, a metal atom, or NR). 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 ( is H or an organic group).

[0082] R 7 For example, H or C 1-10 The organic group is preferably H or C 1-4 The organic group is more preferably H or C 1-4 A alkyl group is even more preferred.

[0083] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0084] For M, H, metal atoms, or NR 7 4 is preferred, and H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, H, Na, K or NH4 is even more preferred, and H, Na or NH4 is particularly preferred.

[0085] For A, -COOM or -SO3M is preferred.

[0086] Examples of monomers represented by general formula (1) include general formula (1a): CX2 = CFCF2 - O - (CF(CF3)CF2O) n5 -CF(CF3)-A (1a) A monomer represented by (wherein each X is the same and represents either F or H; n5 represents 0 or an integer from 1 to 10; and A is the same as defined above) is given as an example.

[0087] In general formula (1a), n5 is preferably 0 or an integer from 1 to 5, more preferably 0, 1, or 2, and even more preferably 0 or 1, in that it is possible to obtain particles with a small primary particle diameter.

[0088] 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 a monomer represented by general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)

[0089] Specifically, the monomer represented by formula (1A) is the general formula

[0090] [ka]

[0091] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 H or F;Z respectively 4 H, F, or CF3; p1+q1+r1 are integers from 0 to 10; s1 are 0 or 1; t1 are integers from 0 to 5, where Z 3 and Z 4 When both are H, a monomer represented by p1+q1+r1+s1 is not 0 (A is the same as in the definition above) can be given. More specifically,

[0092] [ka]

[0093] These are some of the preferred options, among others

[0094] [ka]

[0095] It is preferable that this be the case.

[0096] The monomer represented by the general formula (1A) is preferably -COOM, and in particular, at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is the same as defined above), with CH2=CFCF2OCF(CF3)COOM being more preferred.

[0097] Furthermore, monomers represented by general formula (1) include those represented by the following formula. CF2 = CFCF2 - O - Rf - A (In the formula, Rf and A are the same as above)

[0098] More specifically, [ka] These are some examples.

[0099] It is also preferable that monomer (I) is monomer (2) represented by general formula (2). The fluoropolymer is also preferably a fluoropolymer (2) that includes a polymerization unit (I) based on a monomer (2) represented by general formula (2). CX2 = CY(-O-Rf-A) (2) (In the formula, X is either H or F, either the same or different; Y is H, F, an alkyl group, or a fluorinated alkyl group; Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and possessing an ether linkage or a keto group. A is the same as described above.)

[0100] In general formula (2), X is either H or F. X may be both F, or at least one of them may be H. For example, one may be F and the other H, or both may be H.

[0101] In general formula (2), Y is H, F, an alkyl group, or a fluorine-containing alkyl group. An alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. A fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Y is preferably H, F, or CF3, and more preferably F.

[0102] In general formula (2), it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be H and Y and Z may be F.

[0103] In general formula (2), Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, a fluorinated alkylene group having 2 to 100 carbon atoms and possessing an ether bond, or a fluorinated alkylene group having 2 to 100 carbon atoms and possessing a keto group. Note that the fluorinated alkylene group having 2 to 100 carbon atoms and possessing an ether bond does not include a structure in which the oxygen atom is terminal, and is an alkylene group that contains an ether bond between carbon atoms.

[0104] The number of carbon atoms in the fluorinated alkylene group of Rf is preferably 2 or more. It is also preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less. Examples of fluorinated alkylene groups include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, -CF2CF2CF2-, CF2CF2CF2CF2-, etc. The fluorinated alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0105] The number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 3 or more. Furthermore, the number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less. The fluorinated alkylene group having the ether bond described above is, for example, a general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 H or F;Z respectively 4 It is also preferable that is a divalent base represented by H, F, or CF3; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0106] Specifically, the above fluorine-containing alkylene groups having an ether bond include -CF2CF(CF3)OCF2-, -CF2CF(CF3)OCF2CF2-, -CF2CF(CF3)OCF2CF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, and -(CF(CF3)CF2-O) n -CF(CF3)- (where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having the above ether bond is preferably a perfluoroalkylene group.

[0107] The number of carbon atoms in the fluorinated alkylene group having the keto group is preferably 3 or more. Furthermore, the number of carbon atoms in the fluorinated alkylene group having the keto group is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less.

[0108] Specific examples of the fluorine-containing alkylene group having the keto group mentioned above include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, and -CF2CF(CF3)CO-CF2CF2CF2CF2-. The fluorine-containing alkylene group having the keto group is preferably a perfluoroalkylene group.

[0109] Water may be added to the keto group in the fluorinated alkylene group. Therefore, the monomer (2) may be a hydrate. Examples of the fluorinated 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.

[0110] The monomer represented by the general formula (2) is preferably at least one selected from the group consisting of the monomers represented by the general formulas (2a), (2b), (2c), (2d), (2e), (2f), and (2g). CF2=CF-O-(CF2) n1 -A (2a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) CF2=CF-O-(CF2C(CF3)F) n2 -A (2b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as the above definition.) CF2=CF-O-(CFX 1 ) n3 -A (2c) (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, and A is the same as the above definition.) CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -A (2d) (In the formula, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and A and X 1 are the same as the above definitions.) CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-A (2e) (In the formula, n5 represents an integer of 0 to 10, and A and X 1 are the same as the above definitions.) 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 defined above.) 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 defined above.)

[0111] In general formula (2a), n1 is preferably an integer less than or equal to 5, and more preferably an integer less than or equal to 2.

[0112] Examples of monomers represented by general formula (2a) include CF2=CF-O-CF2COOM, CF2=CF(OCF2CF2COOM), CF2=CF(O(CF2)3COOM), CF2=CF(OCF2CF2SO3M), CF2=CFOCF2SO3M, and CF2=CFOCF2CF2CF2SO3M (wherein M is the same as defined above).

[0113] In general formula (2b), n2 is preferably an integer of 3 or less in terms of the dispersion stability of the resulting composition.

[0114] In general formula (2c), n3 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is preferably H, Na, or NH4.

[0115] In general formula (2d), X 1 In terms of the dispersion stability of the composition, n4 is preferably -CF3, n4 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is preferably H, Na, or NH4.

[0116] Examples of monomers represented by general formula (2d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2COOM, CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2SO3M, CF2=CFOCF2CF(CF3)OCF2CF2SO3M, and CF2=CFOCF2CF(CF3)OCF2CF2CF2SO3M (wherein M represents H, NH4, or an alkali metal).

[0117] In general formula (2e), n5 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is preferably H or NH4.

[0118] Examples of monomers represented by the general formula (2e) include CF2 = CFOCF2CF2CF2COOM (wherein M represents H, Na, NH4, or an alkali metal).

[0119] In general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM or -SO3M, and more preferably -COOM. M is preferably H, Na, K or NH4.

[0120] Examples of monomers represented by the general formula (2f) include CF2 = CF-O-(CF2)3-O-CF2-COOM (wherein M represents H, NH4, or an alkali metal).

[0121] In the general formula (2g), n9 is preferably an integer of 3 or less in terms of water solubility, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, A is preferably -COOM or -SO3M, with -COOM being more preferred, and M is preferably H, Na, K or NH4.

[0122] Examples of monomers represented by the general formula (2g) include CF2=CFO(CF2)2OCF(CF3)COOM, CF2=CFOCF2CF2OCF(CF3)CF2OCF(CF3)COOM, CF2=CFOCF2CF(CF3)OCF2CF2OCF(CF3)COOM, CF2=CF[OCF2CF(CF3)]2O(CF2)2O[CF(CF3)CF2O]CF(CF3)COOM, and CF2=CF[OCF2CF(CF3)]3O(CF2)2O[CF(CF3)CF2O]3CF(CF3)COOM (wherein M represents H, NH4, or an alkali metal).

[0123] It is also preferable that monomer (I) is monomer (3) represented by general formula (3). The fluoropolymer is also preferably a fluoropolymer (3) that includes a polymerization unit (I) based on a monomer (3) represented by general formula (3). CX2 = CY(-Rf-A) (3) (In the formula, X is either -H or F, either the same or different; Y is -H, -F, an alkyl group, or a fluorine-containing alkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having 2 to 100 carbon atoms and possessing an ether bond. A is the same as described above.)

[0124] Furthermore, fluorine-containing alkylene groups having ether bonds with 2 to 100 carbon atoms do not include structures where the oxygen atom is at the terminal end, and are alkylene groups that contain ether bonds between carbon atoms.

[0125] In general formula (3), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In general formula (3), at least one of X and Y is preferably a fluorine atom.

[0126] The monomer represented by general formula (3) is general formula (3a): CF2 = CF - (CF2) n1 -A (3a) (In the formula, n1 represents an integer of 1 to 10, and A is the same as defined above.) The monomer represented by, and the general formula (3b): CF2=CF-(CF2C(CF3)F) n2 -A (3b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as defined above.) At least one selected from the group consisting of monomers represented by is preferable.

[0127] In the general formula (3a) and the general formula (3b), A is preferably -SO3M or COOM, 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 is preferable. R 7 represents H or an organic group.

[0128] 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 preferably -COOM, and M is preferably H or NH4.

[0129] Examples of the monomer represented by the general formula (3a) include CF2=CFCF2COOM (where M is the same as defined above).

[0130] In the general formula (3b), n2 is preferably an integer of 3 or less in terms of the dispersion stability of the resulting composition, A is preferably -COOM, and M is preferably H or NH4.

[0131] Next, a preferable configuration when m is an integer of 2 or more in the general formula (I) will be described.

[0132] 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 fluoropolymer is also preferably a polymer (4) comprising a polymerization unit (4) based on at least one monomer selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). CF2 = CF - CF2 - OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4a) (In the formula, Z 1 , Z 2 And A is the same as the definition above, Q F1 and Q F2 (These are the same or different fluorinated alkylene groups which may contain single bonds, ether bonds between carbon-carbons, or fluorinated oxyalkylene groups which may contain ether bonds between carbon-carbons.) CF2 = CF - OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4b) (In the formula, Z 1 , Z 2 A, Q F1 and Q F2 (This is the same as the definition above.)

[0133] The monomers represented by general formulas (4a) and (4b) are: [ka] These are some examples.

[0134] As monomer (I), at least one selected from the group consisting of monomer (1), monomer (2), and monomer (3) is preferred, more preferably at least one selected from the group consisting of monomer (1) and monomer (2), even more preferably monomer (2), and still more preferably monomer (2a) represented by general formula (2a). As the fluoropolymer, at least one selected from the group consisting of fluoropolymer (1), fluoropolymer (2), and fluoropolymer (3) is preferred, more preferably at least one selected from the group consisting of fluoropolymer (1) and fluoropolymer (2), and even more preferably fluoropolymer (2).

[0135] The fluoropolymers of this disclosure may be copolymers consisting only of polymerization units (I) and polymerization units (II), or they may be copolymers comprising polymerization units (I) and polymerization units (II) and polymerization units based on monomers (I) and other monomers copolymerizable with monomers (II). Polymerization units (I) may be the same or different in each occurrence, and the fluoropolymer may contain polymerization units (I) based on two or more different monomers (I) represented by general formula (I).

[0136] Other monomers that are preferred include those represented by the general formula CFR=CR2 (wherein R is independently H, F, or a perfluoroalkyl group having 1 to 4 carbon atoms, excluding CHF=CHF). Furthermore, fluorine-containing ethylenic monomers having 2 or 3 carbon atoms are also preferred. Examples of other monomers include CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E-isomer), and CHF=CHCF3 (Z-isomer).

[0137] In particular, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2) is preferred due to its good copolymerizability, and at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride is more preferred. Therefore, the polymerization units based on the above other monomers are preferably polymerization units based on tetrafluoroethylene. The polymerization units based on the above other monomers may be the same or different in each appearance, and the fluoropolymer may contain polymerization units based on two or more different other monomers.

[0138] Other monomers mentioned above include, and also, general formula (n1-2):

[0139] [ka]

[0140] (In the formula, X 1 , X 2 H or F;X are the same or different 3 is H, F, Cl, CH3 or CF3;X 4 , X 5 Rf is either the same or different, H or F; a and c are either the same or different, 0 or 1. 3 Examples include monomers represented by fluorine-containing alkyl groups having 1 to 40 carbon atoms or fluorine-containing alkyl groups having 2 to 100 carbon atoms and ether bonds.

[0141] Specifically, 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 Examples of suitable values ​​include those that are the same as those in the above formula (n1-2).

[0142] Other monomers mentioned above include those in formula (n2-1):

[0143] [ka]

[0144] (In the formula, X 9 is H or CH3;Rf 4 Examples include fluorine-containing acrylate monomers represented by a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond. 4 The basis is,

[0145] [ka]

[0146] Examples include (where d3 is an integer from 1 to 4; e3 is an integer from 1 to 10) and so on.

[0147] Other monomers mentioned above include those in formula (n2-2): CH2=CHO-Rf 5 (n2-2) (In the formula, Rf 5 Examples include fluorinated vinyl ethers represented by a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having 2 to 100 carbon atoms and an ether bond.

[0148] Specifically, as monomers of the general formula (n²-2),

[0149] [ka]

[0150] (where e6 is an integer from 1 to 10) is a preferred example.

[0151] More specifically,

[0152] [ka]

[0153] These are some examples.

[0154] Other general formulas (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (In the formula, Rf 6 Fluorine-containing allyl ethers represented by a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond, general formula (n2-4): CH2=CH-Rf 7 (n2-4) (In the formula, Rf 7 Examples 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 2 to 100 carbon atoms and an ether bond.

[0155] Specifically, monomers represented by general formulas (n2-3) and (n2-4) are:

[0156] [ka]

[0157] Examples of monomers include the following.

[0158] The lower limit of the polymerization unit (I) content in fluoropolymers is, in order of preference, 20 mol% or more, 40 mol% or more, and 45 mol% or more relative to the total polymerization units constituting the fluoropolymer, as this further improves water solubility. The upper limit of the polymerization unit (I) content in fluoropolymers is, in order of preference, 99 mol% or less, 90 mol% or less, and 80 mol% or less relative to the total polymerization units constituting the fluoropolymer, because the decomposition initiation temperature becomes even higher.

[0159] The lower limit of the polymerization unit (II) content in fluoropolymers is, in order of preference, 1 mol% or more, 10 mol% or more, and 20 mol% or more, relative to the total polymerization units constituting the fluoropolymer, because the decomposition initiation temperature is higher. The upper limit of the polymer content of polymerization units (I) in fluoropolymers is, in order of preference, 80 mol% or less, 60 mol% or less, and 55 mol% or less relative to the total polymerization units constituting the fluoropolymer, as this further improves water solubility.

[0160] In fluoropolymers, the upper limits for the content of polymerization units based on monomer (I) and other monomers copolymerizable with monomer (II) are 59 mol% or less, 45 mol% or less, 35 mol% or less, 25 mol% or less, 15 mol% or less, 5 mol% or less, and 1 mol% or less.

[0161] The lower limit of the number-average molecular weight of fluoropolymers is, in order of preference, 0.3 × 10⁻⁶. 4 The above is 0.4 × 10 4 The above is 0.5 × 10 4 The above is 0.7 × 10 4 The above is 0.8 × 10 4 The above is 1.0 × 10 4 The above is 1.2 × 10 4 The above is 1.4 × 10 4 , 1.6×10 4 The above is 1.8 × 10 4 The above is 2.0 × 10 4 The above is 3.0 × 10 4 The above is 4.0 × 10 4 That concludes the explanation. The upper limit of the number-average molecular weight of the fluoropolymer is, in order of preference, 75.0 × 10⁻⁶. 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 Below, 30.0 × 10 4 Below, 20.0 × 10 4 The following applies:

[0162] The lower limit of the weight-average molecular weight of fluoropolymers is, in order of preference, 0.4 × 10⁻⁶. 4 The above is 0.5 × 10 4 The above is 0.6 × 10 4The above is 0.8 × 10 4 The above is 1.0 × 10 4 The above is 1.2 × 10 4 The above is 1.4 × 10 4 The above is 1.7 × 10 4 The above is 1.9 × 10 4 The above is 2.1 × 10 4 The above is 2.3 × 10 4 The above is 2.7 × 10 4 The above is 3.1 × 10 4 The above is 3.5 × 10 4 The above is 3.9 × 10 4 The above is 4.3 × 10 4 The above is 4.7 × 10 4 The above is 5.1 × 10 4 The above is 9.0 x 10 4 The above is 15.0 × 10 4 The above is 20.0 × 10 4 The above is 25.0 × 10 4 That concludes the explanation. The upper limit of the weight-average molecular weight of the fluoropolymer is, in order of preference, 150.0 × 10⁻⁶. 4 Below, 100.0 × 10 4 Below, 60.0 × 10 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 The following applies:

[0163] The molecular weight distribution (Mw / Mn) of the fluoropolymer is, in order of preference, 3.0 or less, 2.7 or less, 2.4 or less, 2.2 or less, 2.0 or less, 1.9 or less, 1.7 or less, 1.5 or less, 1.4 or less, and 1.3 or less.

[0164] The number-average molecular weight and weight-average molecular weight are values ​​calculated using gel permeation chromatography (GPC), with monodisperse polystyrene as the standard. If GPC measurement is not possible, the number-average molecular weight of the fluoropolymer can be determined by the correlation between the number-average molecular weight calculated from the number of end 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.

[0165] The acid value of the fluoropolymer is preferably 60 or higher, more preferably 90 or higher, even more preferably 120 or higher, particularly preferably 150 or higher, most preferably 180 or higher, and there is no particular upper limit, but it is preferably 300 or lower.

[0166] The acid value of a fluoropolymer depends on whether the fluoropolymer has acid-type functional groups other than acid-type functional groups such as -SO3H and -COOH (for example, -SO3M, -COOM, etc., where M is a metal atom, -NR). 7 4. If it contains optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, the acid acid type functional group can be converted to the acid type functional group, and then measured by acid-base titration of the acid type functional group.

[0167] Fluoropolymers typically have end groups. These end groups are generated during polymerization, and typical end groups are independently selected from hydrogen, iodine, bromine, linear or branched alkyl groups, and linear or branched fluoroalkyl groups, and may optionally contain at least one additional catenary heteroatom. The alkyl or fluoroalkyl group preferably has 1 to 20 carbon atoms. These end groups are generally generated from initiators or chain transfer agents used in the formation of fluoropolymers, or during chain transfer reactions.

[0168] Fluoropolymers are preferably given an ion exchange rate (IXR) of 43 or less. The IXR is defined as the number of carbon atoms in the polymer backbone relative to the ionic group. Precursor groups that become ionic upon hydrolysis (e.g., -SO2F) are not considered ionic groups for the purpose of determining the IXR.

[0169] IXR is preferably 0.5 or higher, more preferably 1 or higher, even more preferably 3 or higher, even more preferably 4 or higher, and particularly preferably 5 or higher. Furthermore, IXR is even more preferably 33 or lower, particularly preferably 23 or lower, especially preferably 12 or lower, and most preferably 10 or lower.

[0170] The preferred ion exchange capacities of fluoropolymers are, in order of preference, 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.20 meq / g or more, 2.50 meq / g or more, 2.750 meq / g or more, 3.00 meq / g or more, 3.20 meq / g or more, 3.50 meq / g or more, 4.0 meq / g or more, 4.50 meq / g or more, and 5.00 meq / g or more. The ion exchange capacity is the content of ionic groups (anionic groups) in the fluoropolymer and can be calculated from the composition of the fluoropolymer.

[0171] In fluoropolymers, ionic groups (anionic groups) are typically distributed along the polymer backbone. Fluoropolymers preferably contain a polymer backbone along with repeating side chains bonded to it, and these side chains have ionic groups.

[0172] Fluoropolymers are preferably water-soluble. Water solubility means the property of readily dissolving or dispersing in an aqueous medium. Water-soluble fluoropolymers, for example, cannot have their particle size measured by dynamic light scattering (DLS), or exhibit a particle size of 10 nm or less.

[0173] It is preferable that the fluoropolymer has sufficient water solubility. Generally, the higher the fluoropolymer content in an aqueous solution, the more difficult it becomes for the fluoropolymer to dissolve or disperse sufficiently in the aqueous medium. Therefore, even at high concentrations in an aqueous solution, fluoropolymers whose particle size cannot be measured by dynamic light scattering (DLS) can be said to have high water solubility. It is preferable that the particle size cannot be measured even when the fluoropolymer is contained in an aqueous solution at a content of 1.0% by mass. More preferably, it is preferable that the particle size cannot be measured even when the fluoropolymer is contained in an aqueous solution at a content of 1.5% by mass, and even more preferably at 2.0% by mass.

[0174] The viscosity of the aqueous solution of the fluoropolymer is preferably 5.0 mPa.s or higher, more preferably 8.0 mPa.s or higher, even more preferably 10.0 mPa.s or higher, particularly preferably 12.0 mPa.s or higher, most preferably 14.0 mPa.s or higher, preferably 100.0 mPa.s or lower, more preferably 50.0 mPa.s or lower, even more preferably 25.0 mPa.s or lower, and especially preferably 20.0 mPa.s or lower.

[0175] The viscosity of an aqueous solution of a fluoropolymer can be determined by adjusting the fluoropolymer content in the aqueous solution to 33% by mass relative to the aqueous solution, and then measuring the viscosity of the resulting aqueous solution at 20°C using a tuning fork vibrating viscometer (model: SV-10) manufactured by A&D Company, Limited.

[0176] The critical micelle concentration (CMC) of the fluoropolymer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0177] The critical micelle concentration of fluoropolymers can be determined by measuring the surface tension. Surface tension can be measured, for example, using a surface tension meter, model CBVP-A3, manufactured by Kyowa Interface Chemical Co., Ltd.

[0178] Aqueous solutions containing a fluoropolymer and an aqueous medium can be used for various applications. The fluoropolymer content in the aqueous solution is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, particularly preferably 2.0% by mass or more, even more preferably 5.0% by mass or more, most preferably 10% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the aqueous solution.

[0179] Fluoropolymers or aqueous solutions containing fluoropolymers may be substantially free of monomer (I) dimers and trimers. Monomer (I) dimers and trimers are usually produced when monomer (I) is polymerized to obtain fluoropolymers. The content of dimers and trimers in the fluoropolymer is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, even more preferably 0.001% by mass or less, and particularly preferably 0.0001% by mass or less, relative to the fluoropolymer.

[0180] Fluoropolymers or aqueous solutions containing fluoropolymers may be substantially free of dimers and trimers composed of monomer (I) and monomer (II). Dimers and trimers composed of monomer (I) and monomer (II) are usually produced when monomer (I) and monomer (II) are polymerized to obtain fluoropolymers. The content of dimers and trimers in the fluoropolymer is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, even more preferably 0.001% by mass or less, and particularly preferably 0.0001% by mass or less, relative to the fluoropolymer.

[0181] The dimer and trimer content in a fluoropolymer can be determined by performing gel permeation chromatography (GPC) analysis of the fluoropolymer and calculating the ratio (area percentage) of the total peak area of ​​dimers and trimers to the total peak area of ​​each peak in the chromatogram obtained from the GPC analysis.

[0182] Furthermore, if the content of dimers and trimers in the fluoropolymer is less than 0.5% by mass relative to the fluoropolymer, it can be identified by measurement using liquid chromatography-mass spectrometry (LC / MS). Specifically, aqueous solutions containing monomer (I) at five or more levels are prepared, LC / MS analysis is performed on each level, and the relationship between the content and the area (integral value of the peak) is plotted to create a calibration curve for monomer (I). Furthermore, calibration curves for dimers and trimers of monomer (I), or dimers and trimers composed of monomer (I) and monomer (II), are created from the monomer (I) calibration curve. A mixture is prepared by adding methanol to a fluoropolymer, and the mixture is filtered using an ultrafiltration disc (molecular weight cutoff 3000 Da). The resulting recovered solution is then analyzed by LC / MS. Then, using a calibration curve, the area of ​​the chromatogram (integral value of the peak) of the dimer and trimer of monomer (I), or the dimer and trimer composed of monomer (I) and monomer (II), can be converted into the dimer and trimer content, respectively.

[0183] The content of the fraction with a molecular weight of 3000 or less in the fluoropolymer or aqueous solution containing the fluoropolymer may be 3.7% or less, preferably 3.2% or less, more preferably 2.7% or less, even more preferably 1.7% or less, especially preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably 0.5% or less, relative to the fluoropolymer. The lower limit of the content of the fraction with a molecular weight of 3000 or less is not limited, but for example, it is 0.01%. The content of the fraction with a molecular weight of 3000 or less can be calculated by the peak area of ​​GPC. The fraction with a molecular weight of 3000 or less includes all compounds with a molecular weight of 3000 or less.

[0184] The content of the fraction with a molecular weight of 2000 or less in the fluoropolymer or aqueous solution containing the fluoropolymer may be 3.2% or less, preferably 2.7% or less, more preferably 2.2% or less, even more preferably 1.7% or less, especially preferably 1.2% or less, and particularly preferably 0.6% or less, relative to the fluoropolymer. The lower limit of the content of the fraction with a molecular weight of 2000 or less is not limited, but for example, it is 0.01%. The content of the fraction with a molecular weight of 2000 or less can be calculated by the peak area of ​​GPC. The fraction with a molecular weight of 2000 or less includes all compounds with a molecular weight of 2000 or less.

[0185] The content of the fraction with a molecular weight of 1500 or less in the fluoropolymer or aqueous solution containing the fluoropolymer may be 2.7% or less, preferably 2.2% or less, more preferably 1.7% or less, even more preferably 1.2% or less, and especially preferably 0.6% or less, relative to the fluoropolymer. The lower limit of the content of the fraction with a molecular weight of 1500 or less is not limited, but for example, it is 0.01%. The content of the fraction with a molecular weight of 1500 or less can be calculated by the peak area of ​​GPC. The fraction with a molecular weight of 1500 or less includes all compounds with a molecular weight of 1500 or less.

[0186] The content of the fraction with a molecular weight of 1000 or less in the fluoropolymer or aqueous solution containing the fluoropolymer may be 2.2% or less, preferably 1.7% or less, more preferably 1.2% or less, and even more preferably 0.6% or less, relative to the fluoropolymer. The lower limit of the content of the fraction with a molecular weight of 1000 or less is not limited, but for example, it is 0.01%. The content of the fraction with a molecular weight of 1000 or less can be calculated by the peak area of ​​GPC. The fraction with a molecular weight of 1000 or less includes all compounds with a molecular weight of 1000 or less.

[0187] Fluoropolymers or aqueous solutions containing fluoropolymers are preferably substantially free of fluorine-containing surfactants. In this disclosure, "substantially free of fluorine-containing surfactants" means that the content of fluorine-containing surfactants in the fluoropolymer or aqueous solution is 10 ppm by mass or less, preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably 1 ppb by mass or less, and particularly preferably the amount of fluorine-containing surfactants is below the detection limit as measured by liquid chromatography-mass spectrometry (LC / MS).

[0188] The content of fluorine-containing surfactants can be quantified by known methods. For example, it can be quantified by LC / MS analysis. First, methanol is added to the fluoropolymer or aqueous solution, and extraction is performed. The resulting extract is then analyzed by LC / MS. To further improve extraction efficiency, treatments such as Soxhlet extraction or sonication may be performed. From the obtained LC / MS spectrum, molecular weight information is extracted and its agreement with the structural formula of the candidate fluorine-containing surfactant is confirmed. Subsequently, aqueous solutions containing five or more levels of the identified fluorine-containing surfactant were prepared, and LC / MS analysis was performed on each aqueous solution with its respective content. The relationship between the content and the area area corresponding to that content was plotted, and a calibration curve was drawn. Furthermore, using a calibration curve, the area of ​​the LC / MS chromatogram for fluorine-containing surfactants in the extract can be converted to the content of fluorine-containing surfactants.

[0189] Fluorine-containing surfactants will be discussed later in the explanation of the polymerization of monomer (I) and monomer (II).

[0190] (Coating composition) Fluoropolymers or aqueous solutions containing fluoropolymers can be used for a variety of applications. For example, fluoropolymers or aqueous solutions containing fluoropolymers can be suitably used as components of coating compositions.

[0191] The coating composition is preferably a composition containing a fluoropolymer and at least one solvent selected from the group consisting of water and alcohol. By using such a coating composition, a coating film exhibiting excellent anti-reflective properties can be formed. By using a coating composition containing a fluoropolymer with a large amount of polymerization units (I), a uniform coating film with a desired thickness can be easily formed, and the anti-reflective properties and hydrophilicity of the resulting coating film can be enhanced, and a sufficient developer dissolution rate can be obtained. Furthermore, a higher content of polymerization units (I) in the fluoropolymer is preferable because it can impart low refractive index and excellent developer solubility to the coating film.

[0192] The solvent contained in the coating composition is at least one selected from the group consisting of water and alcohol. As the alcohol, a lower alcohol having 1 to 6 carbon atoms is preferred, and at least one selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, and butyl alcohol is more preferred.

[0193] The coating composition may further contain a water-soluble organic solvent (excluding alcohol), at least one basic substance selected from ammonia or organic amines, a surfactant, an acid, a water-soluble polymer, a photoacid generator, an antifoaming agent, a light absorber, a preservative stabilizer, a preservative, an adhesive aid, a dye, and the like.

[0194] The fluoropolymer content in the coating composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, even more preferably 1 to 20% by mass, and particularly preferably 2 to 10% by mass, relative to the coating composition.

[0195] A coating film can be produced by applying a coating composition to a substrate. While there are no particular limitations on the application method of the coating composition, examples include roll coating, casting, dipping, spin coating, water casting, die coating, and the Langmuir-Bludget method.

[0196] Examples of substrates to which the coating composition is applied include silicon wafers and quartz glass.

[0197] In particular, when precise control of film thickness is required, the spin coating method is preferable. When using the spin coating method, the film thickness of the coating film is determined by the rotation speed of the substrate, the rotation time, and the viscosity of the coating composition. Due to the characteristics of the equipment (spin coater), if the rotation speed is too slow or the rotation time is too short, uneven film thickness is likely to occur. Therefore, it is common to coat the coating at a high rotation speed over a certain period of time. However, when a coating composition is applied at a high rotation speed over a certain period of time, the resulting film thickness is small. Therefore, it is not easy to produce a relatively thick film while suppressing film thickness unevenness using the spin coating method. The coating composition of this disclosure contains a fluoropolymer containing a large amount of polymerization units (I), and even when the fluoropolymer is contained at a high concentration, it is possible to form a coating film with a uniform film thickness using the coating composition. This allows for the imparting of excellent effects such as hydrophilicity to the coating film, while simultaneously enabling the easy production of a relatively thick film while suppressing film thickness unevenness.

[0198] The coating film obtained from the coating composition is suitable as, for example, a pellicle or an anti-reflective film. For example, by applying the coating composition onto a photoresist layer, a photoresist laminate comprising a photoresist layer and an anti-reflective film can be produced.

[0199] (Method for producing fluoropolymers) The fluoropolymers of this disclosure can be produced by a manufacturing method for producing fluoropolymers by polymerization of monomer (I) and monomer (II).

[0200] The polymerization temperatures of monomer (I) and monomer (II) are preferably 70°C or lower, more preferably 65°C or lower, even more preferably 60°C or lower, even more preferably 55°C or lower, especially preferably 50°C or lower, particularly preferably 45°C or lower, most preferably 40°C or lower, preferably 10°C or higher, more preferably 15°C or higher, and even more preferably 20°C or higher, in order to easily produce fluoropolymers with even higher molecular weights.

[0201] In the above manufacturing method, monomer (I) and monomer (II) may be copolymerized with the other monomers mentioned above.

[0202] In the above manufacturing method, polymerization may be carried out in the presence of a pH adjusting agent. The pH adjusting agent may be added before polymerization begins or after polymerization begins.

[0203] As pH adjusters, ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium phosphate, potassium phosphate, sodium citrate, potassium citrate, ammonium citrate, sodium gluconate, potassium gluconate, ammonium gluconate, etc. can be used. The above pH can be measured using an Orion pH meter.

[0204] The polymerization pressure is typically around atmospheric pressure to 10 MPaG. The polymerization pressure is determined appropriately depending on the type of monomer used, the molecular weight of the target fluoropolymer, and the reaction rate.

[0205] The polymerization time is typically 1 to 200 hours, but may be 5 to 100 hours.

[0206] In the above manufacturing method, polymerization of monomer (I) and monomer (II) may be carried out in an aqueous medium or in the absence of an aqueous medium. Alternatively, polymerization of monomer (I) and monomer (II) may be carried out in the absence of an aqueous medium, in the presence of a non-aqueous medium (for example, an organic solvent such as toluene) in an amount of less than 10% by mass relative to the amount of monomers containing monomer (I) and monomer (II). Polymerization of monomer (I) and monomer (II) may be carried out by emulsion polymerization or suspension polymerization or by bulk polymerization.

[0207] An aqueous medium is a reaction medium for polymerization and refers to a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as an alcohol, ether, or ketone, and / or a fluorine-containing organic solvent with a boiling point of 40°C or lower. Water is preferred as the aqueous medium.

[0208] The oxygen concentration in the polymerization reaction system is preferably 1500 ppm by volume or less, more preferably 500 ppm by volume or less, even more preferably 100 ppm by volume or less, and particularly preferably 50 ppm by volume or less, in order to easily produce fluoropolymers with even higher molecular weights. Furthermore, the oxygen concentration in the reaction system is usually 0.01 ppm by volume or more. In the above production method, it is preferable that the oxygen concentration in the reaction system is maintained within the above range throughout the entire polymerization period of monomer (I) and monomer (II).

[0209] The oxygen concentration in the polymerization reaction system can be controlled, for example, by circulating an inert gas such as nitrogen or argon, or, in the case of a gaseous monomer, the gaseous monomer, through the liquid or gas phase of the reactor. The oxygen concentration in the polymerization reaction system can also be determined by measuring and analyzing the gas emitted from the exhaust gas line of the polymerization system using a low-concentration oxygen analyzer.

[0210] In the above manufacturing method, polymerization of monomer (I) and monomer (II) can be carried out in the presence of a polymerization initiator. The polymerization initiator is not particularly limited as long as it can generate radicals within the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, polymerization can also be initiated as a redox by combining it with a reducing agent, etc. The concentration of the polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the target fluoropolymer, and the reaction rate. When polymerization of monomer (I) and monomer (II) is carried out in an aqueous medium, it is preferable to use a water-soluble polymerization initiator such as a persulfate. When polymerization of monomer (I) and monomer (II) is carried out in the absence of an aqueous medium, it is preferable to use an oil-soluble polymerization initiator such as a peroxide.

[0211] As polymerization initiators, persulfates (e.g., ammonium persulfate) or organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide can be used alone or in mixtures thereof. They may also be used in combination with reducing agents such as sodium sulfite to form a redox system. Furthermore, during polymerization, radical scavengers such as hydroquinone and catechol, or peroxide decomposition agents such as ammonium sulfite, can be added to adjust the radical concentration in the system.

[0212] As polymerization initiators, persulfates are preferred because they allow for the easy production of fluoropolymers with even higher molecular weights. Examples of persulfates include ammonium persulfate, potassium persulfate, and sodium persulfate, with ammonium persulfate being preferred.

[0213] An oil-soluble radical polymerization initiator may be used as the polymerization initiator. The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, such as dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as dit-butyl peroxide. Also, di(ω-hydro-dodecafluorohexanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, and di(ω-chloro Di[perfluoro(or fluorochloro)acyl]peroxides such as -hexafluorobutyryl)peroxide, di(ω-chloro-decafluorohexanoyl)peroxide, di(ω-chloro-tetradecafluorooctanoyl)peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl)peroxide, di(trichlorooctafluorohexanoyl)peroxide, di(tetrachloroundafluorooctanoyl)peroxide, di(pentachlorotetradecafluorodecanoyl)peroxide, and di(undachlorodotriacontafluorodocosanoyl)peroxide are typical examples.

[0214] There are no particular limitations on the amount of polymerization initiator added, but it is sufficient to add at least an amount that does not significantly reduce the polymerization rate (for example, a few ppm relative to water concentration) in one lump sum at the beginning of polymerization, or sequentially or continuously. The upper limit is a range in which the reaction temperature can be increased while removing heat from the apparatus surface using the heat of the polymerization reaction, and a more preferable upper limit is a range in which the heat of the polymerization reaction can be removed from the apparatus surface.

[0215] In the above manufacturing method, the polymerization initiator can be added at the start of polymerization and also during polymerization. The ratio of the amount of polymerization initiator added at the start of polymerization to the amount of polymerization initiator added during polymerization is preferably 95 / 5 to 5 / 95, more preferably 60 / 40 to 10 / 90, and even more preferably 30 / 70 to 15 / 85. The method of adding the polymerization initiator during polymerization is not particularly limited; the entire amount may be added at once, divided into two or more additions, or added continuously.

[0216] In the above manufacturing method, since fluoropolymers with even higher molecular weights can be easily produced, it is preferable that the total amount of polymerization initiator added for polymerization is 0.00001 to 10% by mass relative to the aqueous medium. The total amount of polymerization initiator added for polymerization is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, preferably 5% by mass or less, and more preferably 2% by mass or less.

[0217] In the above manufacturing method, since fluoropolymers with even higher molecular weights can be easily produced, it is preferable that the total amount of polymerization initiator added for polymerization is 0.001 to 10 mol% relative to the total amount of monomer added for polymerization. The total amount of polymerization initiator added for polymerization is more preferably 0.005 mol% or more, even more preferably 0.01 mol% or more, especially preferably 0.1 mol% or more, most preferably 0.5 mol% or more, more preferably 10 mol% or less, even more preferably 5.0 mol% or less, especially preferably 2.5 mol% or less, most preferably 2.2 mol% or less, and most preferably 2.0 mol% or less.

[0218] In the above manufacturing method, it is preferable that the amount of monomers containing monomer (I) and monomer (II) at the start of polymerization is 20% by mass or more relative to the amount of aqueous medium, since a fluoropolymer with an even higher molecular weight can be easily produced. The amount of monomers is more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular upper limit to the amount of monomers, but from the viewpoint of ensuring smooth polymerization, it may be 200% by mass or less. The amount of monomers at the start of polymerization refers to the total amount of monomer (I) and monomer (II), and any other monomers present in the reactor at the start of polymerization.

[0219] When polymerization of monomer (I) and monomer (II) is carried out in the absence of an aqueous medium, the total amount of polymerization initiator such as peroxide added is preferably 0.001 to 10 mol% of the total amount of monomer (monomer mixture) containing monomer (I) and monomer (II). The total amount of polymerization initiator used for polymerization is more preferably 0.005 mol% or more, even more preferably 0.01 mol% or more, more preferably 10 mol% or less, even more preferably 5.0 mol% or less, especially preferably 2.5 mol% or less, most preferably 2.2 mol% or less, and preferably 2.0 mol% or less.

[0220] Polymerization of monomer (I) and monomer (II) can be carried out by charging an aqueous medium, monomer (I), monomer (II), and optionally other monomers and optionally other additives into a reactor, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of polymerization initiator to start the polymerization reaction. After the start of the polymerization reaction, monomers, polymerization initiators, and other additives may be added as needed.

[0221] Polymerization of monomer (I) and monomer (II) can be carried out substantially in the absence of a fluorine-containing surfactant. In this disclosure, "substantially in the absence of a fluorine-containing surfactant" means that the amount of fluorine-containing surfactant in the aqueous medium is 10 ppm by mass or less. The amount of fluorine-containing surfactant in the aqueous medium is preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably 10 ppb by mass or less, and even more preferably 1 ppb by mass or less.

[0222] Examples of the above-mentioned fluorine-containing surfactants include anionic fluorine-containing surfactants. The above-mentioned anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms with a total number of carbon atoms of 20 or less in the part excluding the anionic group.

[0223] The above-mentioned fluorine-containing surfactant may also be a surfactant containing fluorine with a molecular weight of 1000 or less in the anionic portion. The above-mentioned "anionic portion" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF2) represented by formula (I) described later. n1 In the case of COOM, "F(CF2)" n1 This is the "COO" part.

[0224] The above-mentioned fluorine-containing surfactants also include fluorine-containing surfactants with a LogPOW of 3.5 or less. The above LogPOW is the partition coefficient between 1-octanol and water, and is expressed as LogP [wherein P represents the ratio of the concentration of the fluorine-containing surfactant in octanol to the concentration of the fluorine-containing surfactant in water when a 1:1 mixture of octanol and water containing the fluorine-containing surfactant undergoes phase separation]. The above LogPOW is calculated by performing HPLC on standard substances with known octanol / water partition coefficients (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) under the following conditions: column; TOSOH ODS-120T column (φ4.6 mm × 250 mm, manufactured by Tosoh Corporation), eluent; acetonitrile / 0.6 mass% HClO4 water = 1 / 1 (vol / vol%), flow rate; 1.0 ml / min, sample volume; 300 μL, column temperature; 40°C, detection light; UV 210 nm. A calibration curve is created between the elution time and the known octanol / water partition coefficient, and the LogPOW is calculated from the elution time of the sample solution using this calibration curve.

[0225] Specifically, the above-mentioned fluorine-containing surfactants include U.S. Patent Publication No. 2007 / 0015864, U.S. Patent Publication No. 2007 / 0015865, U.S. Patent Publication No. 2007 / 0015866, U.S. Patent Publication No. 2007 / 0276103, U.S. Patent Publication No. 2007 / 0117914, U.S. Patent Publication No. 2007 / 142541, U.S. Patent Publication No. 2008 / 0015319, and U.S. Patent No. 3250808. Examples include those described in the book, U.S. Patent No. 3,271,341, Japanese Patent Publication No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, Japanese Patent Publication No. 2007-119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, and International Publication No. 2013 / 189826.

[0226] The above anionic fluorine-containing surfactants include those with the following general formula (N0 ): X n0 -Rf n0 -Y 0 (N 0 ) (In the formula, X n0 Rf is H, Cl, or F. n0 This is an alkylene group having 3 to 20 carbon atoms, being linear, branched, or cyclic, in which some or all of the hydrogen atoms are substituted with fluorine, and the alkylene group may contain one or more ether bonds, and some of the hydrogen atoms may be substituted with chlorine. 0 The group is an anionic group. Examples of compounds represented by ) are shown. Y 0 The anionic group may be -COOM, -SO2M, or -SO3M. M is H, a metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 is either H or an organic group. Examples of the above-mentioned metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li. R 7 For example, H or C 1-10 The organic group may be H or C 1-4 The organic group may be H or C 1-4 It may be an alkyl group. M is H, a metal atom, or NR 7 It may be 4, and may be H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 It may be 4, and may be H, Na, K, Li, or NH4. The above Rf n0 It is acceptable if 50% or more of the H atoms are replaced with fluorine.

[0227] The above general formula (N 0 Compounds represented by ) include: The following general formula (N 1 ): Xn0 -(CF2) m1 -Y 0 (N 1 ) (In the formula, X n0 These are H, Cl, and F, and m1 is an integer from 3 to 15, Y 0 This is defined above. ) A compound represented by the following general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 ) (In the formula, Rf n1 m2 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer from 0 to 3, and X n1 is F or CF3, and Y 0 This is defined above. ) A compound represented by the following general formula (N 3 ): Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 ) (In the formula, Rf n2 m3 is a partially or fully fluorinated alkyl group that may contain ether bonds between 1 and 13 carbon atoms, and m3 is an integer between 1 and 3, and Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, where q is 0 or 1, and Y 0 This is defined above. ) A compound represented by the following general formula (N 4 ): Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 ) (In the formula, Rf n4 Y is a linear or branched portion that may contain ether bonds and / or chlorine atoms with 1 to 12 carbon atoms, or a fully fluorinated alkyl group. n1 and Y n2is the same or different, H or F, p is 0 or 1, Y 0 This refers to the compounds represented by the above definition, and the general formula (N 5 ): [ka] (In the formula, X n2 , X n3 and X n4 Rf is a linear or branched portion that may contain H, F, or an ether bond having 1 to 6 carbon atoms, or a fully fluorinated alkyl group, and may be the same or different. n5 L is a linear or branched moiety or a fully fluorinated alkylene group that may contain ether bonds with 1 to 3 carbon atoms, L is a linking group, and Y 0 This is defined above. However, X n2 , X n3 , X n4 and Rf n5 The total number of carbon atoms is 18 or less. Examples of compounds represented by ) are shown.

[0228] The above general formula (N 0 More specifically, examples of compounds represented by the formula (XII) include perfluorocarboxylic acid (I) represented by the following general formula (I), ω-H perfluorocarboxylic acid (II) represented by the following general formula (II), perfluoroether carboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by the following general formula (V), perfluoroalkyl sulfonic acid (VI) represented by the following general formula (VII), ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by the following general formula (VIII), alkylalkylene carboxylic acid (IX) represented by the following general formula (IX), fluorocarboxylic acid (X) represented by the following general formula (X), alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI), compound (XII) represented by the following general formula (XII), compound (XIII) represented by the following general formula (XIII), and so on.

[0229] The above perfluorocarboxylic acid (I) is given by the following general formula (I) F(CF2) n1 COOM (I) (In the formula, n1 is an integer between 3 and 14, and M is H, a metal atom, NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (where is H or an organic group.)

[0230] The above ω-H perfluorocarboxylic acid (II) is given by the following general formula (II) H(CF2) n2 COOM (II) (In the formula, n² is an integer between 4 and 15, and M is as defined above.)

[0231] The above perfluoroether carboxylic acid (III) is given by the following general formula (III) Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III) (In the formula, Rf 1 (where n3 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is as defined above.)

[0232] The above perfluoroalkylalkylene carboxylic acid (IV) is the following general formula (IV) Rf 2 (CH2) n4 Rf 3 COOM (IV) (In the formula, Rf 2 Rf is a perfluoroalkyl group having 1 to 5 carbon atoms. 3 (where n4 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer from 1 to 3, and M is as defined above.)

[0233] The above alkoxyfluorocarboxylic acid (V) is given by the following general formula (V) Rf 4 -O-CY 1 Y 2 CF2-COOM (V) (In the formula, Rf 4 Y is a linear or branched portion that may contain ether bonds and / or chlorine atoms with 1 to 12 carbon atoms, or a fully fluorinated alkyl group. 1 and Y 2 ) are the same or different, and are represented by H or F, and M is as defined above.

[0234] The above perfluoroalkyl sulfonic acid (VI) is the following general formula (VI) F(CF2) n5 SO3M (VI) (In the formula, n5 is an integer between 3 and 14, and M is as defined above.)

[0235] The above ω-H perfluorosulfonic acid (VII) is given by the following general formula (VII) H(CF2) n6 SO3M (VII) (In the formula, n6 is an integer between 4 and 14, and M is as defined above.)

[0236] The above perfluoroalkylalkylene sulfonic acid (VIII) is given by the following general formula (VIII) Rf 5 (CH2) n7 SO3M (VIII) (In the formula, Rf 5 (where n7 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer from 1 to 3, and M is as defined above.)

[0237] The above alkylalkylene carboxylic acid (IX) is the following general formula (IX) Rf 6 (CH2) n8 COOM (IX) (In the formula, Rf 6 (where n8 is a linear or branched portion that may contain ether bonds with 1 to 13 carbon atoms, or a fully fluorinated alkyl group, n8 is an integer from 1 to 3, and M is as defined above.)

[0238] The above fluorocarboxylic acid (X) is given by the following general formula (X) Rf 7 -O-Rf 8 -O-CF2-COOM (X) (In the formula, Rf 7 Rf is a linear or branched moiety or a fully fluorinated alkyl group that may contain ether bonds and / or chlorine atoms with 1 to 6 carbon atoms. 8 (where M is a linear or branched portion having 1 to 6 carbon atoms or a fully fluorinated alkyl group, and M is as defined above.)

[0239] The above alkoxyfluorosulfonic acid (XI) is given by the following general formula (XI) Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI) (In the formula, Rf 9 Y is a partially or fully fluorinated alkyl group that may contain ether bonds between 1 to 12 carbon atoms, and may contain chlorine. 1 and Y 2 ) are the same or different, and are represented by H or F, and M is as defined above.

[0240] The above compound (XII) has the following general formula (XII): [ka] (In the formula, X 1 , X 2 and X 3 Rf is a linear or branched portion that may contain H, F and ether bonds having 1 to 6 carbon atoms, or a fully fluorinated alkyl group, and may be the same or different.10 L is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 It is an anionic group. ) Y 0 may be -COOM, -SO2M, or -SO3M, or -SO3M, or COOM (wherein M is as defined above). Examples of L include single bonds, moieties that may contain ether bonds with 1 to 10 carbon atoms, or fully fluorinated alkylene groups.

[0241] The above compound (XIII) has the following general formula (XIII): Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM (XIII) (In the formula, Rf 11 This is represented as follows: is a fluoroalkyl group having 1 to 5 carbon atoms and containing chlorine, n9 is an integer from 0 to 3, n10 is an integer from 0 to 3, and M is as defined above. Compound (XIII) is CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10 One example is CF2COONH4 (a mixture with an average molecular weight of 750, where n9 and n10 are as defined above).

[0242] As mentioned above, examples of the above-mentioned anionic fluorine-containing surfactants include carboxylic acid-based surfactants and sulfonic acid-based surfactants.

[0243] The fluorine-containing surfactant may be a single fluorine-containing surfactant or a mixture containing two or more fluorine-containing surfactants.

[0244] Examples of fluorine-containing surfactants include compounds represented by the following formula. The fluorine-containing surfactant may be a mixture of these compounds. In one embodiment of the polymerization described above, monomer (I) and monomer (II) are polymerized in substantially the absence of the compound represented by the following formula. 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, [ka] (In each formula, M is H, metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (This is either H or an organic group.)

[0245] In the above manufacturing method, monomer (I) and monomer (II) are polymerized in an aqueous medium, so an aqueous solution containing the fluoropolymer and the aqueous medium is usually obtained. The resulting aqueous solution containing the fluoropolymer may be used as is for various purposes, or the fluoropolymer obtained by separating it from the aqueous solution may be used for various purposes. The method for separating the fluoropolymer from the aqueous solution is not particularly limited. For example, the fluoropolymer can be separated by methods such as coagulation, washing, and drying of the fluoropolymer in the aqueous solution.

[0246] The fluoropolymer or aqueous solution obtained by polymerization of monomer (I) and monomer (II) contains fractions with molecular weights of 3000 or less, 2000 or less, 1500 or less, 1000 or less, dimers and trimers of monomer (I), and dimers and trimers composed of monomer (I) and monomer (II). To remove these, the fluoropolymer or aqueous solution obtained by polymerization of monomer (I) and monomer (II) may be subjected to post-treatment.

[0247] For example, in the above manufacturing method, after the polymerization of monomer (I) and monomer (II) is completed, the composition containing the aqueous medium and the fluoropolymer may be recovered, and the obtained composition may be treated by at least one means selected from the group consisting of ultrafiltration, microfiltration, dialysis membrane treatment, liquid-liquidation, and reprecipitation.

[0248] When monomer (I) and monomer (II) are polymerized in the absence of an aqueous medium, a fluoropolymer or a composition containing the fluoropolymer is obtained after polymerization is complete. The fluoropolymer or composition can then be mixed with an aqueous medium, and the resulting aqueous medium and the composition containing the fluoropolymer can be treated by at least one means selected from the group consisting of ultrafiltration, microfiltration, dialysis membrane treatment, liquid-liquid extraction, and reprecipitation.

[0249] Compositions obtained by polymerization of monomer (I) and monomer (II) typically contain more than 1.0% by mass of monomer (I) dimers and trimers in total relative to the mass of the fluoropolymer. The content of monomer (I) dimers and trimers in the fluoropolymer may be, for example, 2.0% by mass or more, 3.0% by mass or more, 30.0% by mass or less, or 20.0% by mass or less, relative to the fluoropolymer. The content of dimers and trimers in a composition can be determined by performing gel permeation chromatography (GPC) analysis of the composition and calculating the ratio (area percentage) of the total peak area of ​​dimers and trimers to the total area of ​​each peak in the chromatogram obtained by GPC analysis.

[0250] Compositions obtained by polymerization of monomer (I) and monomer (II) typically contain dimers and trimers composed of monomer (I) and monomer (II) in a total amount of more than 1.0% by mass relative to the mass of the fluoropolymer. The content of dimers and trimers composed of monomer (I) and monomer (II) in the fluoropolymer may be, for example, 2.0% by mass or more, 3.0% by mass or more, 30.0% by mass or less, or 20.0% by mass or less, relative to the fluoropolymer. The content of dimers and trimers in a composition can be determined by performing gel permeation chromatography (GPC) analysis of the composition and calculating the ratio (area percentage) of the total peak area of ​​the dimers and trimers to the total area of ​​each peak in the chromatogram obtained by GPC analysis.

[0251] Next, the obtained aqueous medium and composition containing the fluoropolymer are recovered, and the obtained composition is preferably treated by at least one means selected from the group consisting of ultrafiltration, microfiltration, dialysis membrane treatment, liquid-liquid extraction, and reprecipitation. This treatment can remove from the composition dimers and trimers of monomer (I), or dimers and trimers composed of monomer (I) and monomer (II), that are contained in the composition obtained by polymerization of monomer (I) and monomer (II). More preferably, the treatment means is at least one means selected from the group consisting of ultrafiltration, microfiltration, liquid-liquid extraction, and reprecipitation, even more preferably at least one means selected from the group consisting of ultrafiltration and liquid-liquid extraction, and ultrafiltration is particularly preferred.

[0252] Polymerization of monomer (I) and monomer (II) produces dimers and trimers of monomer (I), or dimers and trimers composed of monomer (I) and monomer (II), and as a result, dimers and trimers of monomer (I), or dimers and trimers composed of monomer (I) and monomer (II) are contained in the fluoropolymer.

[0253] When removing dimers and trimers, unreacted monomer (I) is usually also removed from the composition. Furthermore, by appropriately selecting post-treatment methods, fractions with molecular weights of 3000 or less, 2000 or less, 1500 or less, and 1000 or less can also be removed.

[0254] The composition obtained by polymerization of monomer (I) and monomer (II) may be the post-polymerization composition, a diluted or concentrated post-polymerization composition, or a composition that has undergone dispersion stabilization treatment. It is also preferable to adjust the viscosity of the composition by ultrafiltration, microfiltration, or dialysis membrane treatment in order to facilitate these processes.

[0255] The fluoropolymer content in the composition is not particularly limited and may be, for example, 0.1 to 40.0% by mass. From the viewpoint of dimer and trimer removal efficiency, the fluoropolymer content in the composition is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, even more preferably 20.0% by mass or less, particularly preferably 10.0% by mass or less, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.2% by mass or more, and particularly preferably 1.5% by mass or more. The fluoropolymer content in the composition can be adjusted, for example, by adding water to a composition obtained by polymerization of monomer (I) and monomer (II), or by concentrating a composition obtained by polymerization of monomer (I) and monomer (II).

[0256] The pH of the composition is preferably -7.0 to 11.0, more preferably -6.0 to 8.0, and even more preferably -5.0 to 7.0. The pH of the composition can be adjusted by adding a pH adjusting agent to the composition obtained by polymerization of monomer (I) and monomer (II). The pH adjusting agent may be an acid or an alkali, and examples include phosphates, sodium hydroxide, potassium hydroxide, and aqueous ammonia.

[0257] When ultrafiltration, microfiltration, or dialysis membrane treatment is performed, the viscosity of the composition is preferably 25 mPa·s or less, so that these treatments proceed smoothly. The viscosity of the composition can be adjusted, for example, by adjusting the weight-average molecular weight and number-average molecular weight of the fluoropolymer, by adjusting the concentration of the fluoropolymer in the composition, or by adjusting the temperature of the composition.

[0258] The above ultrafiltration or microfiltration can be either a cross-flow or dead-end method, but the cross-flow method is preferred from the viewpoint of reducing membrane clogging.

[0259] The above-mentioned ultrafiltration can be performed using an ultrafiltration membrane. For example, ultrafiltration can be performed using an ultrafiltration apparatus having an ultrafiltration membrane, and centrifugal ultrafiltration, batch ultrafiltration, circulating ultrafiltration, etc., can be employed.

[0260] The molecular weight cutoff of the above ultrafiltration membrane is typically 0.1 × 10⁻⁶. 4 ~30×10 4 The molecular weight is approximately Da. The above ultrafiltration membrane suppresses membrane clogging and can efficiently reduce dimers and trimers, resulting in a fractional molecular weight of 0.3 × 10⁻⁶. 4 It is preferable that the molecular weight is greater than or equal to Da. The above fractional molecular weight is 0.5 × 10 4 Da or higher is more preferable, 0.8 × 10 4 Da or higher is particularly preferred, 1.0 × 10 4 A value of Da or higher is most preferable. The above fractionated molecular weight is 1.0 × 10⁻⁶. 4 It may be greater than Da. Furthermore, the above fractionation molecular weight is 20 × 10 from the viewpoint of dimer and trimer removal efficiency. 4 Preferably 10 × 10 4 Da or lower is preferable.

[0261] The molecular weight cutoff of the ultrafiltration membrane described above can be determined, for example, by passing water through the membrane with polystyrene of known weight-average molecular weight and selecting the molecular weight cutoff that blocks 90% of the polystyrene. The quantitative determination of polystyrene can be performed using gel permeation chromatography.

[0262] The shape of the ultrafiltration membrane described above is not limited to conventionally known shapes, but examples include hollow fiber type, flat membrane type, spiral type, and tubular type. From the viewpoint of preventing clogging, the hollow fiber type is preferred. The inner diameter of the hollow fiber ultrafiltration membrane is not limited, but may be, for example, 0.1 to 2 mm. Preferably, it is 0.8 to 1.4 mm. The length of the hollow fiber ultrafiltration membrane is not limited, but may be, for example, 0.05 to 3 m. Preferably, it is 0.05 to 2 m.

[0263] The material of the ultrafiltration membrane is not particularly limited, but examples include organic materials such as cellulose, cellulose ester, polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, chlorinated polyethylene, polypropylene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyacrylonitrile, polyvinylidene fluoride, and polytetrafluoroethylene; metals such as stainless steel; or inorganic materials such as ceramics. The material of the ultrafiltration membrane is preferably an organic material, more preferably chlorinated polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, polysulfone, or polyethersulfone, and even more preferably polyacrylonitrile, polysulfone, or polyvinylidene fluoride.

[0264] Specific examples of the ultrafiltration membranes mentioned above include DESAL's G-5, G-10, G-20, G-50, PW, and HWS UF types; KOCH's HFM-180, HFM-183, HFM-251, HFM-300, HFM-116, HFM-183, HFM-300, HFK-131, HFK-328, MPT-U20, MPS-U20P, and MPS-U20S; Synder's SPE1, SPE3, SPE5, SPE10, SPE30, SPV5, SPV50, and SOW30; Asahi Kasei's Microza® UF series; and Nitto Denko's NTR7410.

[0265] The above ultrafiltration is preferably performed at a pressure of 0.01 MPa or higher from the viewpoint of dimer and trimmer removal efficiency. More preferably, it is 0.03 MPa or higher, and even more preferably 0.05 MPa or higher. Furthermore, from the viewpoint of pressure resistance, the above pressure is preferably 0.5 MPa or lower, more preferably 0.25 MPa or lower, and even more preferably 0.2 MPa or lower.

[0266] From the viewpoint of the removal efficiency of dimers and trimers, the above ultrafiltration is preferably carried out at a flow rate of 10 mL / min or more, more preferably at a flow rate of 50 mL / min or more, more preferably at a flow rate of 5000 mL / min or less, and more preferably at a flow rate of 1000 mL / min or less.

[0267] The above microfiltration can be performed using a microfiltration membrane. Microfiltration membranes typically have an average pore size of 0.05 to 1.0 μm. The above-mentioned microfiltration membrane can efficiently remove dimers and trimers, so it is preferable that the average pore size is 0.1 μm or more. More preferably, it is 0.075 μm or more, and even more preferably, 0.1 μm or more. Furthermore, it is preferable that the average pore size is 1.00 μm or less. More preferably, the average pore size is 0.50 μm or less, and even more preferably, 0.25 μm or less. The average pore size of the above-mentioned microfiltration membrane can be measured in accordance with ASTM F 316-03 (bubble point method).

[0268] The shape of the above-mentioned microfiltration membrane can be any conventionally known shape, but is not limited to those mentioned above. Examples include hollow fiber type, flat membrane type, spiral type, tubular type, etc. From the viewpoint of preventing clogging, the hollow fiber type is preferred. The inner diameter of the hollow fiber type microfiltration membrane is not limited, but may be, for example, 0.1 to 2 mm. Preferably, it is 0.8 to 1.4 mm. The length of the hollow fiber type microfiltration membrane is not limited, but may be, for example, 0.05 to 3 m. Preferably, it is 0.05 to 2 m.

[0269] Examples of materials for the above-mentioned microfiltration membrane include cellulose-based materials, aromatic polyamides, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, polytetrafluoroethylene, ceramics, and metals. Among these, aromatic polyamides, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, or polytetrafluoroethylene are preferred, and polyacrylonitrile or polyvinylidene fluoride are particularly preferred.

[0270] Examples of precision filtration membranes include Cefilt from NGK Insulators, Inc.; Microza U series and Microza P series from Asahi Kasei Corporation; Poaflon SPMW, Poaflon OPMW, and Poaflon PM from Sumitomo Electric Industries, Ltd.; Toray Industries, Inc.'s Torefil; NADIR MP005 and NADIR MV020 from Microdyne Nadia Corporation; and X-flow from Norit Corporation.

[0271] The above-mentioned microfiltration is preferably performed at a pressure of 0.01 MPa or higher from the viewpoint of the removal efficiency of dimers and trimmers. More preferably, it is 0.03 MPa or higher, and even more preferably 0.05 MPa or higher. Furthermore, from the viewpoint of pressure resistance, the above pressure is preferably 0.5 MPa or lower, more preferably 0.25 MPa or lower, and even more preferably 0.2 MPa or lower.

[0272] From the viewpoint of dimer and trimer removal efficiency, the above microfiltration is preferably carried out at a flow rate of 10 mL / min or more, more preferably at a flow rate of 50 mL / min or more, more preferably at a flow rate of 5000 mL / min or less, and more preferably at a flow rate of 1000 mL / min or less.

[0273] The above dialysis membrane treatment is performed using a dialysis membrane. The dialysis membrane is typically 0.05 × 10⁻⁶. 4 ~100×10 4 It has a fractional molecular weight of Da. The above dialysis membrane suppresses membrane clogging and can efficiently remove dimers and trimers, resulting in a fractional molecular weight of 0.3 × 10⁻⁶. 4 It is preferable that the molecular weight is greater than or equal to Da. The above fractional molecular weight is 0.5 × 10 4 Da or higher is more preferable, 0.8 × 10 4 Da or higher is even preferable, 1.0 × 10 4 A molecular weight of Da or higher is even more preferable. The above fractional molecular weight is 1.0 × 10⁻⁶. 4 It can be Da or higher. Furthermore, the above fractionation molecular weight is 20 × 10 from the viewpoint of dimer and trimer removal efficiency. 4 Preferably less than or equal to Da, 10 × 10 4 Da or lower is preferable. The molecular weight cutoff of the above-mentioned dialysis membrane can be measured, for example, by the same method as for an ultrafiltration membrane.

[0274] The material of the dialysis membrane mentioned above is not particularly limited, but examples include cellulose, polyacrylonitrile, polymethyl methacrylate, ethylene vinyl alcohol copolymer, polysulfone, polyamide, and polyester polymer alloy.

[0275] Examples of dialysis membranes include Spectra / Por(registered trademark) Float-A-Lyzer, Tube-A-Lyzer, Dialysis tubing, 6Dialysis tubing, and 7Dialysis tubing, all manufactured by Spectrum Laboratories.

[0276] The above ultrafiltration, microfiltration, or dialysis membrane treatment is preferably carried out at a temperature of 10°C or higher. More preferably, it is 15°C or higher, even more preferably 20°C or higher, and particularly preferably 30°C or higher. By setting the temperature within the above range, dimers and trimers can be reduced more efficiently. The above temperature is preferably 90°C or lower, more preferably 80°C or lower, even more preferably 70°C or lower, and particularly preferably 60°C or lower.

[0277] Ultrafiltration, microfiltration, or dialysis membrane treatment can be performed while adding water to the composition or while adjusting the pH of the composition. Water may be added to the composition intermittently or continuously.

[0278] The endpoint of ultrafiltration, microfiltration, or dialysis membrane treatment can be determined as appropriate and is not limited. Furthermore, to improve the durability of the filtration membrane, the ultrafiltration, microfiltration, or dialysis membrane treatment may be backwashed with water once, approximately every 1 to 24 hours.

[0279] Liquid-liquid separation can be carried out, for example, by adding an organic solvent to the composition, separating it into two phases, an aqueous phase and an organic solvent phase, and recovering the aqueous phase.

[0280] Reprecipitation can be carried out, for example, by dropping the composition into a poor solvent to precipitate the fluoropolymer, recovering the precipitated fluoropolymer, dissolving the recovered fluoropolymer in a good solvent, dropping the resulting solution into a poor solvent to precipitate the fluoropolymer again, and recovering the precipitated fluoropolymer.

[0281] By post-treating a composition containing a fluoropolymer using the above-described means, an aqueous solution containing a fluoropolymer that is substantially free of dimers and trimers, or an aqueous solution containing a fluoropolymer with a reduced content of fractions with a molecular weight of 3000 or less, can usually be obtained. The aqueous solution containing the fluoropolymer obtained by treating the composition may be used as is for various applications, or the fluoropolymer obtained by separating it from the aqueous solution may be used for various applications. The method for separating the fluoropolymer from the aqueous solution is not particularly limited. For example, the fluoropolymer can be separated by methods such as coagulation, washing, and drying of the fluoropolymer in the aqueous solution.

[0282] By the manufacturing method described above, a fluoropolymer or an aqueous solution containing a fluoropolymer and an aqueous medium can be obtained.

[0283] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0284] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.

[0285] Each value in the examples was measured by the following method.

[0286] (Concentration of fluoropolymer in aqueous solution (solids content concentration)) Approximately 1 g of an aqueous solution containing a fluoropolymer was dried in a vacuum dryer at 60°C for 60 minutes. The mass of the residue after heating was measured, and the percentage of the mass of the residue after heating relative to the mass of the aqueous solution (1 g) was used.

[0287] (Composition of fluoropolymers) 19 The measurement was performed using F-NMR.

[0288] (Method for measuring the content of weight-average molecular weight (Mw), number-average molecular weight (Mn), and fractions with a molecular weight of 3000 or less) The Mw and Mn of fluoropolymers were determined by gel permeation chromatography (GPC) equipped with a differential refractive index detector (Showa Denko RI-501), using two connected columns from Tosoh Corporation (one TSKgel α-M and one TSG gel α-3000), flowing 0.05 M lithium bromide-doped dimethylformamide as the solvent at a flow rate of 0.8 ml / min, and calculating the molecular weight using monodisperse polystyrene as the standard.

[0289] (Method for measuring the content of dimers and trimers in fluoropolymers) (1) Extraction from aqueous solution The solid content of the aqueous solution of the fluoropolymer was measured, and an amount of the aqueous solution corresponding to 0.2 g of solid content of the fluoropolymer was weighed. Then, water and methanol were added to the aqueous solution so that the volume ratio of water to methanol was 50 / 50 (vol%), obtaining a mixture containing the fluoropolymer, water, and methanol. Subsequently, the obtained mixture was filtered using an ultrafiltration disc (molecular weight cutoff 3000 Da) to recover the recovered solution containing the fluoropolymer. The recovered solution was analyzed using a liquid chromatograph-mass spectrometer (Waters, LC-MS ACQUITY UPLC / TQD) to obtain a chromatogram of the recovered solution. The dimer and trimer content in the recovered solution was determined by converting the integral values ​​of the dimer and trimer-derived peaks appearing in the chromatogram of the recovered solution to monomer dimer and trimer content using a calibration curve for related monomers.

[0290] (2) Calibration curve for monomers Five levels of methanol standard solutions of monomers with known concentrations ranging from 1 ng / mL to 100 ng / mL were prepared and measured using a liquid chromatograph-mass spectrometer (Waters, LC-MS ACQUITY UPLC / TQD). The relationship between the concentration of each monomer and the integral value of the peak relative to that concentration was plotted to create a calibration curve (first-order approximation) for each monomer. Next, calibration curves for the dimers and trimers of each monomer were created using the calibration curves (first-order approximations) for each monomer.

[0291] Measurement equipment configuration and LC-MS measurement conditions [Table 1]

[0292] The limit of quantification in this measuring instrument configuration is 1 ng / mL.

[0293] Example 1 6.32 g of CF2=CFOCF2CF2SO3Na, 34 g of water, and ammonium persulfate (APS) equivalent to 1.5 mol% of the amount of CF2=CFOCF2CF2SO3Na were added to the reactor, and 3.58 g of 1,2-difluoroethylene was introduced. The mixture was then stirred at 60°C for 7.5 hours under a sealed container. The reactor pressure decreased from 0.30 MPa to 0.23 MPa as the reaction progressed.

[0294] The aqueous solution containing the obtained fluoropolymer was placed in a dialysis membrane (molecular weight cutoff 3500 Da, made of cellulose), and dialysis was performed by contacting it with water at room temperature to obtain an aqueous solution of the fluoropolymer. The concentration of the fluoropolymer in the aqueous solution obtained by dialysis membrane purification was 1.4% by mass.

[0295] When the aqueous solution obtained by dialysis was analyzed by NMR to determine the polymer composition, the molar ratio of polymerization units based on CF2=CFOCF2CF2SO3Na and polymerization units based on 1,2-difluoroethylene in the fluoropolymer was found to be 1.0 / 1.1.

[0296] Furthermore, the weight-average molecular weight (Mw) of the obtained fluoropolymer was 9.7 × 10⁻⁶. 4 The number-average molecular weight (Mn) is 5.0 × 10⁻⁶. 4 The content of dimers and trimers of CF2=CFOCF2CF2SO3Na in the aqueous solution obtained by dialysis was 0.1% by mass or less relative to the fluoropolymer. Furthermore, the content of dimers and trimers composed of CF2=CFOCF2CF2SO3Na and CHF=CHF was 0.1% by mass or less relative to the fluoropolymer. The content of fractions with a molecular weight of 3000 or less in the aqueous solution obtained by dialysis was 0.1% by mass or less.

[0297] Furthermore, TG-DTA analysis of the dried fluoropolymer revealed that the decomposition initiation temperature was 355°C.

[0298] Using the obtained fluoropolymer, several aqueous solutions with different fluoropolymer content were prepared. When the particle size of each aqueous solution was measured by dynamic light scattering (DLS), no particle size could be measured when the fluoropolymer content was 8.2% by mass or less relative to the aqueous solution. Therefore, the fluoropolymer obtained in Example 1 has high water solubility.

[0299] The results of the TG-DTA analysis of the obtained fluoropolymer were found to be that the homopolymer of CF2=CFOCF2CF2SO3Na (weight-average molecular weight (Mw) is 0.9 × 10⁻⁶). 4 The results of the TG-DTA analysis of the fluoropolymer are shown in Figure 1. From the results shown in Figure 1, it can be seen that the fluoropolymer obtained in Example 1 decomposes more readily above the decomposition onset temperature compared to the homopolymer of CF2=CFOCF2CF2SO3Na.

[0300] Example 2 In a reactor, 1.28 g of CH2=CFCF2OCF(CF3)COOH, 7.9 g of acetonitrile, and an amount of perbutyl PV (registered trademark, manufactured by NOF Corporation) equivalent to 1 mol% of the CH2=CFCF2OCF(CF3)COOH were added. Then, 1.72 g of 1,2-difluoroethylene was introduced, and the mixture was stirred at 55°C for 19 hours under a sealed container. The reactor pressure decreased from 0.22 MPa to 0.11 MPa as the reaction progressed.

[0301] An arbitrary amount of KOH aqueous solution was added to the aqueous solution containing the obtained fluoropolymer. After distillation off the acetonitrile, the aqueous solution containing the base-treated fluoropolymer was placed on a dialysis membrane (molecular weight cutoff 3500 Da, made of cellulose), and dialysis was performed by contacting it with water at room temperature to obtain an aqueous solution of fluoropolymer. The concentration of fluoropolymer in the aqueous solution obtained by dialysis membrane purification was 1.9% by mass.

[0302] When the aqueous solution obtained by dialysis was analyzed by NMR to determine the polymer composition, the molar ratio of polymerization units based on CH2=CFCF2OCF(CF3)COOH and polymerization units based on 1,2-difluoroethylene in the fluoropolymer was found to be 1.0 / 1.0.

[0303] Furthermore, the weight-average molecular weight (Mw) of the obtained fluoropolymer was 2.1 × 10⁻⁶. 5 The number-average molecular weight (Mn) is 1.2 × 10⁻⁶. 5 The content of dimers and trimers of CH2=CFCF2OCF(CF3)COOH in the aqueous solution obtained by dialysis was 0.1% by mass or less relative to the fluoropolymer. Furthermore, the content of dimers and trimers composed of CH2=CFCF2OCF(CF3)COOH and CHF=CHF was 0.1% by mass or less relative to the fluoropolymer. The content of fractions with a molecular weight of 3000 or less in the aqueous solution obtained by dialysis was 0.1% by mass or less.

[0304] Example 3 In a reactor, 1.28 g of CH2=CFCF2OCF(CF3)COOH, 7.9 g of acetonitrile, and an amount of perbutyl PV (registered trademark, manufactured by NOF Corporation) equivalent to 1 mol% of the CH2=CFCF2OCF(CF3)COOH were added. Then, 4.13 g of 1,2-difluoroethylene was introduced, and the mixture was stirred at 55°C for 20 hours under a sealed condition. The reactor pressure decreased from 0.31 MPa to 0.15 MPa as the reaction progressed.

[0305] An arbitrary amount of KOH aqueous solution was added to the aqueous solution containing the obtained fluoropolymer. After distillation off the acetonitrile, the aqueous solution containing the base-treated fluoropolymer was placed on a dialysis membrane (molecular weight cutoff 3500 Da, made of cellulose), and dialysis was performed by contacting it with water at room temperature to obtain an aqueous solution of fluoropolymer. The concentration of fluoropolymer in the aqueous solution obtained by dialysis membrane purification was 2.3% by mass.

[0306] When the aqueous solution obtained by dialysis was analyzed by NMR to determine the polymer composition, the molar ratio of polymerization units based on CH2=CFCF2OCF(CF3)COOH and polymerization units based on 1,2-difluoroethylene in the fluoropolymer was found to be 3.0 / 1.0.

[0307] Furthermore, the weight-average molecular weight (Mw) of the obtained fluoropolymer was 1.2 × 10⁻⁶. 5 The number-average molecular weight (Mn) is 3.0 × 10⁻⁶. 4 The content of dimers and trimers of CH2=CFCF2OCF(CF3)COOH in the aqueous solution obtained by dialysis was 0.1% by mass or less relative to the fluoropolymer. Furthermore, the content of dimers and trimers composed of CH2=CFCF2OCF(CF3)COOH and CHF=CHF was 0.1% by mass or less relative to the fluoropolymer. The content of fractions with a molecular weight of 3000 or less in the aqueous solution obtained by dialysis was 0.1% by mass or less.

[0308] Example 4 In a reactor, 1.28 g of CH2=CFCF2OCF(CF3)COOH, 7.9 g of acetonitrile, and an amount of perbutyl PV (registered trademark, manufactured by NOF Corporation) equivalent to 3 mol% of the CH2=CFCF2OCF(CF3)COOH were added. 1.45 g of 1,2-difluoroethylene was then introduced, and the mixture was stirred at 55°C for 19 hours under a sealed container. The reactor pressure decreased from 0.12 MPa to 0.06 MPa as the reaction progressed.

[0309] An arbitrary amount of KOH aqueous solution was added to the aqueous solution containing the obtained fluoropolymer. After distillation off the acetonitrile, the aqueous solution containing the base-treated fluoropolymer was placed on a dialysis membrane (molecular weight cutoff 3500 Da, made of cellulose), and dialysis was performed by contacting it with water at room temperature to obtain an aqueous solution of fluoropolymer. The concentration of fluoropolymer in the aqueous solution obtained by dialysis membrane purification was 2.2% by mass.

[0310] When the aqueous solution obtained by dialysis was analyzed by NMR to determine the polymer composition, the molar ratio of polymerization units based on CH2=CFCF2OCF(CF3)COOH and polymerization units based on 1,2-difluoroethylene in the fluoropolymer was found to be 0.7 / 1.0.

[0311] Furthermore, the weight-average molecular weight (Mw) of the obtained fluoropolymer was 1.3 × 10⁻⁶. 5 The number-average molecular weight (Mn) is 8.0 × 10⁻⁶. 4 The content of dimers and trimers of CH2=CFCF2OCF(CF3)COOH in the aqueous solution obtained by dialysis was 0.1% by mass or less relative to the fluoropolymer. Furthermore, the content of dimers and trimers composed of CH2=CFCF2OCF(CF3)COOH and CHF=CHF was 0.1% by mass or less relative to the fluoropolymer. The content of fractions with a molecular weight of 3000 or less in the aqueous solution obtained by dialysis was 0.1% by mass or less.

Claims

1. A fluoropolymer containing polymerization units (I) based on monomer (I) represented by general formula (I), and polymerization units (II) based on monomer (II) represented by formula (II). CX １ X ３ =CX ２ R(-CZ １ Z ２ -A ０ ) ｍ (I) (wherein X １ and X ３ are each independently F or H; X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is -COOM, -SO₃M, -OSO₃M or -C(CF₃)₂OM (M is H, a metal atom, NR₇₄, an imidazolium optionally having a substituent, a pyridinium optionally having a substituent or a phosphonium optionally having a substituent, and R₇ is H or a C₁₋₁₀ alkyl group.); R is a hydrocarbon group having 1 to 100 carbon atoms in which some or all of the hydrogen atoms bonded to the carbon atoms may contain an ether bond or a keto group and are substituted with fluorine; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; m is 1.) CHF=CHF (II)

2. The fluoropolymer according to claim 1, wherein the content of polymerization unit (I) is 20 to 99 mol% relative to the total polymerization units constituting the fluoropolymer, and the content of polymerization unit (II) is 80 to 1 mol% relative to the total polymerization units constituting the fluoropolymer.

3. The fluoropolymer according to claim 1, wherein the content of polymerization unit (I) is 40 to 99 mol% of the total polymerization units constituting the fluoropolymer, and the content of polymerization unit (II) is 60 to 1 mol% of the total polymerization units constituting the fluoropolymer.

4. The fluoropolymer according to claim 1, wherein the content of dimers and trimers of monomer (I) is 1.0% by mass or less relative to the fluoropolymer.

5. The fluoropolymer according to claim 1, wherein the content of dimers and trimers composed of monomer (I) and monomer (II) is 1.0% by mass or less relative to the fluoropolymer.

6. A ０ However, -SO ３ M or -COOM (where M is H, a metal atom, NR) ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, R ７ The fluoropolymer according to claim 1, wherein is an alkyl group of H or C1-10.

7. The fluoropolymer according to claim 1, wherein the polymerization unit (I) is at least one selected from the group consisting of polymerization unit (1) based on monomer (1) represented by general formula (1) and polymerization unit (2) based on monomer (2) represented by general formula (2). CX ２ =CY(-CZ ２ -O-Rf-A) (1) (In the formula, X is H or F, either the same or different; Y is H, F, an alkyl group, or a fluorinated alkyl group; Z is H, F, an alkyl group, or a fluoroalkyl group, either the same or different; Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO ３ M, -OSO ３ M or -C (CF ３ ) ２ OM (M is H, metal atom, NR) ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, R ７ (wherein X, Y, and Z are H or C1-10 alkyl groups, at least one of X, Y, and Z contains a fluorine atom.) CX ２ =CY(-O-Rf-A) (2) (In the formula, X is either H or F, either the same or different; 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 having 2 to 100 carbon atoms. A is the same as described above.)

8. A is -SO ３ M or -COOM (where M is H, a metal atom, NR) ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, R ７ The fluoropolymer according to claim 7, wherein is an alkyl group of H or C1-10.

9. The weight-average molecular weight (Mw) is 1.0 × 10⁻⁶. ４ The fluoropolymer according to claim 1, wherein the above is true.

10. The fluoropolymer according to claim 1, wherein the molecular weight distribution (Mw / Mn) is 3.0 or less.

11. The fluoropolymer according to claim 1, wherein the ion exchange capacity is 0.8 meq / g or more.

12. The fluoropolymer according to claim 1, wherein the ion exchange rate (IXR) is 43 or less.

13. An aqueous solution containing the fluoropolymer described in claim 1.

14. The aqueous solution according to claim 13, wherein the content of the fluoropolymer is 1.0% by mass or more relative to the aqueous solution.

15. A coating composition containing the fluoropolymer described in claim 1, or the aqueous solution described in claim 13.

16. A method for producing a fluoropolymer according to claim 1, comprising polymerizing monomer (I) and monomer (II) to obtain the fluoropolymer.

17. The manufacturing method according to claim 16, wherein the polymerization temperature is 70°C or lower.

18. The manufacturing method according to claim 16, wherein the polymerization is carried out in an aqueous medium.

19. The manufacturing method according to claim 16, wherein the polymerization is carried out in the presence of a polymerization initiator, and the polymerization initiator is a persulfate.

20. The manufacturing method according to claim 16, wherein the polymerization is carried out in an aqueous medium in the presence of a polymerization initiator, and the total amount of the polymerization initiator used in the polymerization is 0.00001 to 10% by mass relative to the aqueous medium.

21. The manufacturing method according to claim 16, wherein the polymerization is carried out in an aqueous medium, and after the polymerization is completed, the composition containing the aqueous medium and the fluoropolymer is recovered, and the composition is treated by at least one means selected from the group consisting of ultrafiltration, microfiltration, dialysis membrane treatment, liquid-liquid separation and reprecipitation.

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