Method for producing fluorine-containing polymer

Abstract

Provided is a method for producing a fluorine-containing polymer, the method comprising: a step in which a monomer (I) represented by general formula (I) is polymerized in an aqueous medium in the absence of a fluorine-containing surfactant (excluding the monomer (I) represented by general formula (I)) substantially, thereby obtaining a crude composition of a polymer containing the monomer (I); a step for obtaining a polymer (I) in which the content of the dimer and the trimer of the monomer (I) is 1.0 mass% or less relative to the polymer (I) by removing the dimer and the trimer of the monomer (I) contained in the crude composition from the crude composition; and a step for obtaining a fluorine-containing polymer by polymerizing a fluorine-containing monomer in an aqueous medium in the presence of the polymer (I). CX1X3 = CX2R (-CZ1Z2-A0) m (I) (In the formula, X1 and X3 are each independently F, Cl, H, or CF3; x2 is H, F, alkyl or fluorine-containing alkyl; a0 is an anionic group; r is a linking group; z1 and Z2 are each independently H, F, alkyl or fluorine-containing alkyl; and m is an integer of 1 or more. ).

Description

[0001] This application is a divisional application. The application number of the original application is 202080078031.2, the application date is November 19, 2020, and the name of the invention is “Method for producing fluorinated polymers”. Technical Field

[0002] The present invention relates to a method for producing a fluorine-containing polymer. Background Art

[0003] Patent Document 1 describes particles comprising agglomerates of a fluorinated polymer and a core of a fluorinated ionomer.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2010 / 075494 Summary of the invention

[0007] Problems to be solved by the invention

[0008] An object of the present invention is to provide a method for producing a fluorinated polymer which contains substantially no dimers or trimers of monomers constituting a polymer used in polymerization of a fluorinated monomer.

[0009] Means for solving problems

[0010] According to the present invention, there is provided a method for producing a fluorinated polymer, comprising: a step of polymerizing a monomer (I) represented by the general formula (I) in an aqueous medium in the substantial absence of a fluorinated surfactant (excluding the monomer (I) represented by the general formula (I)), thereby obtaining a crude composition of a polymer containing the monomer (I); a step of removing dimers and trimers of the monomer (I) contained in the crude composition from the crude composition, thereby obtaining a polymer (I) having a content of dimers and trimers of the monomer (I) of not more than 1.0% by mass relative to the polymer (I); and a step of polymerizing a fluorinated monomer in an aqueous medium in the presence of the polymer (I), thereby obtaining a fluorinated polymer.

[0011] CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0012] (Where X 1 and X 3 Each independently is F, Cl, H or CF 3 ;X2 is H, F, alkyl or fluorinated alkyl; A 0 is an anionic group; R is a connecting group; Z 1 and Z 2 Each is independently H, F, alkyl or fluorinated alkyl; m is an integer greater than 1.)

[0013] In the production method of the present invention, the molecular weight of the monomer (I) is preferably 500 or less.

[0014] In the general formula (I), A 0 Preferred are -COOM, -SO 3 M, -OSO 3 M or -C(CF 3 ) 2 OM (M is -H, metal atom, -NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0015] In the general formula (I), A 0 Preferably -COOM (M is -H, metal atom, -NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0016] In the production method of the present invention, the monomer (I) is preferably a monomer represented by the general formula (1).

[0017] CX 2 =CY(-CZ 2 -O-Rf-A) (1)

[0018] (wherein, X is the same or different and is -H or F, Y is -H, -F, alkyl or fluorinated alkyl, and Z is the same or different and is -H, -F, alkyl or fluorinated alkyl. 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 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7is H or an organic group. ) wherein at least one of X, Y and Z contains a fluorine atom. )

[0019] In the production method of the present invention, the monomer (I) is preferably a monomer represented by the general formula (1A).

[0020] CH 2 =CF(-CF 2 -O-Rf-A)(1A)

[0021] (wherein, 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 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group. )

[0022] In the general formulae (1) and (1A), A is preferably -COOM (M is -H, a metal atom, -NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group. ).

[0023] In the production method of the present invention, it is preferred to remove dimers and trimers of the monomer (I) from the crude composition by ultrafiltration of the crude composition.

[0024] Effects of the Invention

[0025] According to the present invention, there can be provided a production method capable of producing a fluorinated polymer substantially free of dimers and trimers of monomers constituting a polymer used in polymerization of a fluorinated monomer. DETAILED DESCRIPTION

[0026] Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0027] Before describing the present invention in detail, some terms used in the present invention are defined or described.

[0028] In the present invention, fluororesin refers to a partially crystalline fluorine-containing polymer, which is a fluoroplastic. Fluororesin has a melting point, is thermoplastic, and can be melt-processable or non-melt-processable.

[0029] In the present invention, melt processability means that the polymer can be melted and processed using existing processing equipment such as extruders and injection molding machines. Therefore, the melt flow rate of a melt-processable fluororesin measured by the measurement method described below is usually 0.01 g / 10 min to 500 g / 10 min.

[0030] In the present invention, fluororubber refers to an amorphous fluorine-containing polymer. "Amorphous" means that the size of the melting peak (ΔH) appearing in the differential scanning calorimetry [DSC] (heating temperature 10°C / min) or differential thermal analysis [DTA] (heating rate 10°C / min) of the fluoropolymer is less than 4.5 J / g. Fluororubber exhibits elastomeric properties by cross-linking. Elastomeric properties refer to the following properties: the polymer can be stretched and can maintain its original length when the force required to stretch the polymer is no longer applied.

[0031] In the present invention, the partially fluorinated rubber refers to a fluorinated polymer containing fluorinated monomer units and perfluorinated monomer units in an amount of less than 90 mol % relative to all polymerized units, and has a glass transition temperature of 20° C. or less and a melting peak (ΔH) of 4.5 J / g or less.

[0032] In the present invention, perfluoro rubber (perfluoroelastomer) refers to a fluorine-containing polymer in which the content of perfluoro monomer units relative to all polymerized units is 90 mol% or more, preferably 91 mol% or more, and has a glass transition temperature of 20°C or less and a melting peak (ΔH) of 4.5 J / g or less, and further, a polymer in which the concentration of fluorine atoms contained in the fluorine-containing polymer is 71% by mass or more, preferably 71.5% by mass or more. In the present invention, the concentration of fluorine atoms contained in the fluorine-containing polymer is calculated from the type and content of each monomer constituting the fluorine-containing polymer to obtain the concentration (mass %) of fluorine atoms contained in the fluorine-containing polymer.

[0033] In the present invention, a perfluoromonomer refers to a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule. The above-mentioned perfluoromonomer may also be a monomer in which several fluorine atoms bonded to carbon atoms are replaced by chlorine atoms in addition to carbon atoms and fluorine atoms, or a monomer that has nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms or silicon atoms in addition to carbon atoms. As the above-mentioned perfluoromonomer, a monomer in which all hydrogen atoms are replaced by fluorine atoms is preferred. The above-mentioned perfluoromonomer does not contain a monomer that provides a crosslinking site.

[0034] The monomer providing a crosslinking site is a monomer having a crosslinking group (curing site monomer) which provides a crosslinking site for forming a crosslink with a curing agent to the fluorine-containing polymer.

[0035] In the present invention, the polytetrafluoroethylene [PTFE] is preferably a fluorine-containing polymer in which the content of tetrafluoroethylene is 99 mol % or more based on all polymerized units.

[0036] In the present invention, both the fluororesin (excluding polytetrafluoroethylene) and the fluororubber are preferably fluorine-containing polymers containing less than 99 mol % of tetrafluoroethylene based on all polymerized units.

[0037] In the present invention, the content of each monomer constituting the fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis and fluorescent X-ray analysis according to the types of monomers.

[0038] In the present invention, the "organic group" refers to a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound.

[0039] Examples of the "organic group" include:

[0040] an alkyl group which may have one or more substituents,

[0041] an alkenyl group which may have one or more substituents,

[0042] an alkynyl group which may have one or more substituents,

[0043] a cycloalkyl group which may have one or more substituents,

[0044] a cycloalkenyl group which may have one or more substituents,

[0045] a cycloalkadienyl group which may have one or more substituents,

[0046] an aryl group which may have one or more substituents,

[0047] an aralkyl group which may have one or more substituents,

[0048] a non-aromatic heterocyclic group which may have one or more substituents,

[0049] a heteroaryl group which may have one or more substituents,

[0050] Cyano,

[0051] Formyl,

[0052] RaO-,

[0053] RaCO-,

[0054] RaSO 2 -、

[0055] RaCOO-

[0056] RaNRaCO-,

[0057] RaCONRa-

[0058] RaOCO-,

[0059] RaOSO 2 -,as well as

[0060] R 2 -

[0061] (In these formulas, Ra is independently

[0062] an alkyl group which may have one or more substituents,

[0063] an alkenyl group which may have one or more substituents,

[0064] an alkynyl group which may have one or more substituents,

[0065] a cycloalkyl group which may have one or more substituents,

[0066] a cycloalkenyl group which may have one or more substituents,

[0067] a cycloalkadienyl group which may have one or more substituents,

[0068] an aryl group which may have one or more substituents,

[0069] an aralkyl group which may have one or more substituents,

[0070] A non-aromatic heterocyclic group which may have one or more substituents, or

[0071] a heteroaryl group which may have one or more substituents,

[0072] Rb is independently H or an alkyl group which may have one or more substituents).

[0073] As the organic group, an alkyl group which may have one or more substituents is preferred.

[0074] In the present invention, a "substituent" refers to a group that can be substituted. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamide group, an aromatic sulfonamide group, a heterocyclic sulfonamide group, an amino group, an aliphatic an aliphatic amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thiol group, an aromatic thiol group, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaromatic oxyphosphinyl group.

[0075] The aliphatic group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic group include an alkyl group having a total carbon number of 1 to 8, preferably 1 to 4, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc.

[0076] The 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 thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methylsulfonylphenyl group.

[0077] The heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the heterocyclic group include a 5- to 6-membered heterocyclic ring having a total carbon number of 2 to 12, preferably 2 to 10, such as a 2-tetrahydrofuranyl group and a 2-pyrimidinyl group.

[0078] The 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 thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the acyl group include an acyl group having a total carbon number of 2 to 8, preferably 2 to 4, such as an acetyl group, a propionyl group, a benzoyl group, a 3-pyridinecarbonyl group, etc.

[0079] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. Examples of the acylamino group include acylamino groups having a total carbon number of 2 to 12, preferably 2 to 8, and alkylcarbonylamino groups having a total carbon number of 2 to 8, such as acetylamino groups, benzoylamino groups, 2-pyridinecarbonylamino groups, and propionylamino groups.

[0080] The aliphatic oxycarbonyl group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic oxycarbonyl group include an alkoxycarbonyl group having a total carbon number of 2 to 8, preferably 2 to 4, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, etc.

[0081] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the carbamoyl group include an unsubstituted carbamoyl group and an alkyl carbamoyl group having 2 to 9 carbon atoms in total, preferably an unsubstituted carbamoyl group and an alkyl carbamoyl group having 2 to 5 carbon atoms in total, such as N-methyl carbamoyl group, N,N-dimethyl carbamoyl group, N-phenyl carbamoyl group, etc.

[0082] The aliphatic sulfonyl group may be saturated or unsaturated, and may have a hydroxyl group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic sulfonyl group include an alkylsulfonyl group having a total carbon number of 1 to 6, preferably a total carbon number of 1 to 4, such as a methylsulfonyl group.

[0083] The aromatic sulfonyl group may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic sulfonyl group include an arylsulfonyl group having a total carbon number of 6 to 10, such as a benzenesulfonyl group.

[0084] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group or the like.

[0085] The acylamino group may include, for example, acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino, etc. Examples of the acylamino group include acylamino groups having a total carbon number of 2 to 12, preferably acylamino groups having a total carbon number of 2 to 8, and more preferably alkylcarbonylamino groups having a total carbon number of 2 to 8, such as acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino, etc.

[0086] The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, or the like.

[0087] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 total carbon atoms, a dialkylsulfamoyl group having 2 to 10 total carbon atoms, an arylsulfamoyl group having 7 to 13 total carbon atoms, and a heterocyclic sulfamoyl group having 2 to 12 total carbon atoms. More preferred examples include a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 total carbon atoms, a dialkylsulfamoyl group having 3 to 6 total carbon atoms, an arylsulfamoyl group having 6 to 11 total carbon atoms, and a heterocyclic sulfamoyl group having 2 to 10 total carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, and a 4-pyridylsulfamoyl group.

[0088] The aliphatic oxy group may be saturated or unsaturated, and may include methoxy, ethoxy, isopropoxy, cyclohexyloxy, methoxyethoxy, etc. Examples of the aliphatic oxy group include alkoxy groups having a total carbon number of 1 to 8, preferably 1 to 6, such as methoxy, ethoxy, isopropoxy, cyclohexyloxy, methoxyethoxy, etc.

[0089] The 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 condensed with the aromatic group, or an aliphatic oxycarbonyl group, and preferably may have an aliphatic group having a total carbon number of 1 to 4, an aliphatic oxy group having a total carbon number of 1 to 4, a halogen atom, a carbamoyl group having a total carbon number of 1 to 4, a nitro group, or an aliphatic oxycarbonyl group having a total carbon number of 2 to 4.

[0090] The aliphatic thiol group may be saturated or unsaturated, and examples thereof include alkylthio groups having 1 to 8 total carbon atoms, more preferably 1 to 6 total carbon atoms, such as methylthio, ethylthio, carbamoylmethylthio, tert-butylthio and the like.

[0091] The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoylamino group include carbamoylamino groups, alkylcarbamoylamino groups having 2 to 9 total carbon atoms, dialkylcarbamoylamino groups having 3 to 10 total carbon atoms, arylcarbamoylamino groups having 7 to 13 total carbon atoms, and heterocycliccarbamoylamino groups having 3 to 12 total carbon atoms. Carbamoylamino groups, alkylcarbamoylamino groups having 2 to 7 total carbon atoms, dialkylcarbamoylamino groups having 3 to 6 total carbon atoms, arylcarbamoylamino groups having 7 to 11 total carbon atoms, and heterocycliccarbamoylamino groups having 3 to 10 total carbon atoms are preferred, such as carbamoylamino groups, methylcarbamoylamino groups, N,N-dimethylcarbamoylamino groups, phenylcarbamoylamino groups, and 4-pyridylcarbamoylamino groups.

[0092] In the present invention, the range represented by endpoints includes all the numerical values ​​included in the range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0093] In the present invention, the term "at least 1" includes all numerical values ​​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.).

[0094] Next, the production method of the present invention will be described in detail.

[0095] The manufacturing method of the present invention comprises:

[0096] A step of polymerizing the monomer (I) represented by the general formula (I) in an aqueous medium in the substantial absence of a fluorinated surfactant (excluding the monomer (I) represented by the general formula (I)) to obtain a crude composition containing a polymer of the monomer (I);

[0097] A step of removing dimers and trimers of the monomer (I) contained in the crude composition from the crude composition to obtain a polymer (I) having a content of dimers and trimers of the monomer (I) of 1.0 mass % or less relative to the polymer (I); and

[0098] A step of polymerizing a fluorinated monomer in an aqueous medium in the presence of a polymer (I) to obtain a fluorinated polymer.

[0099] <Polymer (I)>

[0100] The polymer (I) used in the production method of the present invention is a polymer of a monomer (I) represented by the general formula (I), wherein the content of dimers and trimers of the monomer (I) is 1.0 mass % or less relative to the polymer (I).

[0101] CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0102] (Where X 1 and X 3 Each independently is F, Cl, H or CF 3 ;X 2 is H, F, alkyl or fluorinated alkyl; A 0 is an anionic group; R is a connecting group; Z 1 and Z 2 Each is independently H, F, alkyl or fluorinated alkyl; m is an integer greater than 1.)

[0103] As X 2 , preferably F, Cl, H or CF 3 In addition, as Z 1 and Z 2 , preferably F or CF 3 .

[0104] The polymer (I) used in the production method of the present invention does not substantially contain dimers and trimers of the monomer (I). Dimers and trimers of the monomer (I) are usually produced when the monomer (I) is polymerized to obtain the polymer (I). The content of dimers and trimers in the polymer (I) is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, further preferably 0.001% by mass or less, and particularly preferably 0.0001% by mass or less relative to the polymer (I).

[0105] The content of dimers and trimers in polymer (I) can be determined by performing gel permeation chromatography (GPC) analysis of polymer (I) 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.

[0106] When the content of dimers and trimers in the polymer (I) is less than 0.5% by mass based on the polymer (I), the content can be identified by measurement using liquid chromatography-mass spectrometry (LC / MS / MS).

[0107] Specifically, aqueous solutions of five or more levels of the content of the monomer (I) are prepared, and LC / MS / MS analysis is performed on each content, and the relationship between the content and the area (integral value of the peak) relative to the content is plotted to prepare a calibration curve for the monomer (I). Furthermore, calibration curves for dimers and trimers of the monomer (I) are prepared from the calibration curve for the monomer (I).

[0108] Methanol was added to the polymer (I) to prepare a mixture, and an extract (supernatant) was recovered from the mixture by centrifugal separation. The obtained extract was analyzed by LC / MS / MS.

[0109] Then, using the calibration curve, the area of ​​the dimer and trimer chromatogram (integrated value of the peak) of the monomer (I) can be converted into the content of the dimer and trimer.

[0110] By using a polymer (I) substantially free of dimers and trimers during the polymerization of a fluorinated monomer in an aqueous medium, a fluorinated polymer substantially free of dimers and trimers of the monomer (I) can be produced. It was previously unknown that the polymer (I) contained dimers and trimers of the monomer (I) constituting the polymer (I). The present invention first clarified the presence of dimers and trimers of the monomer (I) in the polymer (I), and provided a method for removing them for the first time.

[0111] The polymer (I) is a polymer comprising a polymerized unit (I) based on the monomer (I). The polymer (I) used in the present invention is a polymer obtained by substantially removing dimers (polymers comprising two polymerized units (I)) and trimers (polymers comprising three polymerized units (I)) from a polymer (I) comprising two or more polymerized units (I).

[0112] The molecular weight of the monomer (I) is preferably 500 or less, preferably 400 or less. That is, the polymer (I) preferably does not substantially contain dimers and trimers having a molecular weight of 1500 or less, and more preferably does not substantially contain dimers and trimers having a molecular weight of 1200 or less. It was previously unknown that dimers and trimers of low molecular weight monomer (I) are contained in the polymer (I). The present invention has clarified for the first time the presence of dimers and trimers of low molecular weight monomer (I) in the polymer (I), and the present invention provides for the first time a method for removing them.

[0113] In the present invention, the anionic group includes anionic groups such as sulfate ester group and carboxylate ester group, and also includes acid groups such as -COOH, -COONH 4 As the anionic group, preferably a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group or -C(CF 3 )2 OM (where M is -H, metal atom, -NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0114] In the production method of the present invention, as the monomer (I) represented by the general formula (I), one or two or more monomers can be used.

[0115] The dimer and trimer of the monomer (I) may be a polymer formed from one monomer (I) as the monomer (I) represented by the general formula (I), or may be a copolymer formed from two or more monomers (I) having different structures.

[0116] The polymer (I) may contain only polymerized units (I) based on one monomer (I) represented by the general formula (I), or may contain polymerized units (I) based on two or more monomers (I) represented by the general formula (I).

[0117] The present invention has clarified for the first time the existence of dimers and trimers of the low molecular weight monomer (I) in the polymer (I), and has provided for the first time a method for removing them.

[0118] R is a linking group. In the present invention, a "linking group" is an (m+1)-valent linking group, and when m is 1, it refers to a divalent linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. The upper limit is not limited, for example, it may be 100 or less, or 50 or less.

[0119] The linking group may be a chain or branched, cyclic or acyclic structure, saturated or unsaturated, substituted or unsubstituted, and may contain one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as desired, and may contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, carbamate, urea and carbamate as desired. The above linking group does not contain carbon atoms and may be a chain heteroatom such as oxygen, sulfur or nitrogen.

[0120] m is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1. When m is an integer greater than or equal to 2, Z 1 , Z 2 and A 0 Can be the same or different.

[0121] Next, a preferred structure when m is 1 in the general formula (I) will be described.

[0122] R is preferably a chain hetero atom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0123] When R is a divalent organic group, the hydrogen atom bonded to the carbon atom may be substituted by a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. In addition, R may be either a chain or a branched chain, or may be either a cyclic or acyclic. In addition, R may contain a functional group (e.g., an ester, an ether, a ketone (keto group), an amine, a halide, etc.).

[0124] In addition, R may be a non-fluorinated divalent organic group, or a partially fluorinated or perfluorinated divalent organic group.

[0125] R may be, for example: a hydrocarbon group having no fluorine atom bonded to a carbon atom; a hydrocarbon group having a portion of hydrogen atoms bonded to a carbon atom replaced by fluorine atoms; or a hydrocarbon group having all hydrogen atoms bonded to a carbon atom replaced by fluorine atoms, which may contain oxygen atoms, double bonds, or functional groups.

[0126] R is preferably a hydrocarbon group having 1 to 100 carbon atoms which may contain an ether bond or a keto group, and a part or all of hydrogen atoms bonded to carbon atoms in the hydrocarbon group may be substituted with fluorine.

[0127] As R, it is preferably selected from -(CH 2 ) a -、-(CF 2 ) a -、-O-(CF 2 ) a -、-(CF 2 ) a -O-(CF 2 ) b -、-O(CF 2 ) a -O-(CF 2 ) b -、-(CF 2 ) a -[O-(CF 2 ) b ] c -、-O(CF 2 ) a -[O-(CF 2 ) b ] c -、-[(CF 2 ) a -O] b -[(CF 2 ) c -O] d -、-O[(CF 2 )a -O] b -[(CF 2 ) c -O] d -、-O-[CF 2 CF(CF 3 )O] a -(CF 2 ) b -、-[CF 2 CF(CF 3 )O] a -、-[CF(CF 3 )CF 2 O] a -、-(CF 2 ) a -O-[CF(CF 3 )CF 2 O] a -、-(CF 2 ) a -O-[CF(CF 3 )CF 2 O] a -(CF 2 ) b -、-[CF 2 CF(CF 3 )] a -CO-(CF 2 ) b -, and at least one of their combinations.

[0128] In the formula, a, b, c and d are independently at least 1. a, b, c and d can independently be 2 or more, 3 or more, 4 or more, 10 or more, or 20 or more. The upper limit of a, b, c and d is, for example, 100.

[0129] As R, the general formula (r1) is preferred:

[0130] -CF 2 -O-(CX 6 2 ) e -{O-CF(CF 3 )} f -(O) g -(r1)

[0131] (Where X 6 Each independently is H, F or CF 3 , e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1), preferably a divalent group represented by the general formula (r2):

[0132] -CF 2 -O-(CX 7 2 ) e -(O) g -(r2)

[0133] (Where X 7 Each independently is H, F or CF 3 , e is an integer of 0 to 3, and g is 0 or 1).

[0134] Preferred specific examples of R include -CF 2 -O-, -CF 2 -O-CF 2 -、-CF 2 -O-CH 2 -、-CF 2 -O-CH 2 CF 2 -、-CF 2 -O-CF 2 CF 2 -、-CF 2 -O-CF 2 CH 2 -、-CF 2 -O-CF 2 CF 2 CH 2 -、-CF 2 -O-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -、-CF 2 -O-CF(CF 3 )CF 2 -O-, -CF 2 -O-CF(CF 3 )CF 2 -O-CF 2 -、-CF 2 -O-CF(CF 3 )CH 2 - etc. Among them, R is preferably a perfluoroalkylene group containing or not containing an oxygen atom, specifically, -CF 2 -O-, -CF 2 -O-CF 2 -、-CF 2 -O-CF 2 CF 2 -、-CF 2 -O-CF(CF 3 )-、-CF2 -O-CF(CF 3 )CF 2 -, or -CF 2 -O-CF(CF 3 )CF 2 -O-.

[0135] As -R-CZ of general formula (I) 1 Z 2 -, preferably general formula (s1):

[0136] -CF 2 -O-(CX 6 2 ) e -{O-CF(CF 3 )} f -(O) g -CZ 1 Z 2 -(s1)

[0137] (Where X 6 Each independently is H, F or CF 3 , e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, Z 1 and Z 2 Each independently represents H, F, alkyl or fluorinated alkyl), in formula (s1), Z 1 and Z 2 More preferably, F or CF 3 , and more preferably one is F and the other is CF 3 .

[0138] In the general formula (I), -R-CZ 1 Z 2 -, preferably general formula (s2):

[0139] -CF 2 -O-(CX 7 2 ) e -(O) g -CZ 1 Z 2 -(s2)

[0140] (Where X 7 Each independently is H, F or CF 3 , e is an integer from 0 to 3, g is 0 or 1, Z 1 and Z 2 Each independently represents H, F, alkyl or fluorinated alkyl), in formula (s2), Z 1 and Z 2 More preferably, F or CF3 , further preferably, one is F and the other is CF 3 .

[0141] As -R-CZ in general formula (I) 1 Z 2 -, preferably -CF 2 -O-CF 2 -, -CF 2 -O-CF(CF 3 )-、-CF 2 -O-C(CF 3 ) 2 -, -CF 2 -O-CF 2 -CF 2 -, -CF 2 -O-CF 2 -CF(CF 3 )-、-CF 2 -O-CF 2 -C(CF 3 ) 2 -, -CF 2 -O-CF 2 CF 2 -CF 2 -, -CF 2 -O-CF 2 CF 2 -CF(CF 3 )-、-CF 2 -O-CF 2 CF 2 -C(CF 3 ) 2 -, -CF 2 -O-CF(CF 3 )-CF 2 -, -CF 2 -O-CF(CF 3 )-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )-C(CF 3 ) 2 -, -CF 2 -O-CF(CF 3 )-CF 2 -, -CF 2 -O-CF(CF 3 )-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )-C(CF 3 )2 -、-CF 2 -O-CF(CF 3 )CF 2 -CF 2 -、-CF 2 -O-CF(CF 3 )CF 2 -CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -C(CF 3 ) 2 -、-CF 2 -O-CF(CF 3 )CF 2 -O-CF 2 -、-CF 2 -O-CF(CF 3 )CF 2 -O-CF(CF 3 )-, or -CF 2 -O-CF(CF 3 )CF 2 -OC(CF 3 ) 2 -, more preferably -CF 2 -O-CF(CF 3 )-、-CF 2 -O-CF 2 -CF(CF 3 )-、-CF 2 -O-CF 2 CF 2 -CF(CF 3 )-、-CF 2 -O-CF(CF 3 )-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -CF(CF 3 )-, or -CF 2 -O-CF(CF 3 )CF 2 -O-CF(CF 3 )-.

[0142] Polymer (I) is also preferably highly fluorinated. For example, preferably except for the phosphate moieties (e.g., CH 2 OP(O)(OM) 2 ) and sulfate moieties (e.g., CH 2 OS(O)2 OM) and other anionic groups (A 0 ), more than 80%, more than 90%, more than 95%, or 100% of the CH bonds in the polymer (I) are replaced by CF bonds.

[0143] The monomer (I) and the polymer (I) also preferably have anionic groups (A 0 ) has a CF bond but no CH bond. That is, in the general formula (I), preferably X 1 , X 2 and X 3 All of them are F, R is a perfluoroalkylene group having 1 or more carbon atoms, the perfluoroalkylene group may be any of chain and branched, cyclic and acyclic, and may contain at least one chain heteroatom. The perfluoroalkylene group may have 2 to 20 carbon atoms, or 4 to 18 carbon atoms.

[0144] The monomer (I) and the polymer (I) may also be partially fluorinated. That is, the monomer (I) and the polymer (I) are preferably free of anionic groups (A 0 ) has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0145] Anionic group (A 0 ) can be -SO 3 M, -OSO 3 M, -COOM, -SO 2 NR'CH 2 COOM, -CH 2 OP(O)(OM) 2 、[-CH 2 O] 2 P(O)(OM), -CH 2 CH 2 OP(O)(OM) 2 、[-CH 2 CH 2 O] 2 P(O)(OM), -CH 2 CH 2 OSO 3 M, -P(O)(OM) 2 、-SO 2 NR'CH 2 CH 2 OP(O)(OM) 2 、[-SO 2 NR'CH 2 CH 2 O] 2 P(O)(OM), -CH2 OSO 3 M, -SO 2 NR'CH 2 CH 2 OSO 3 M, or -C(CF 3 ) 2 OM. Among them, -SO is preferred 3 M, -OSO 3 M, -COOM, -P(O)(OM) 2 or -C(CF 3 ) 2 OM, more preferably -COOM, -SO 3 M, -OSO 3 M or -C(CF 3 ) 2 OM, more preferably -SO 3 M, -COOM or -P(O)(OM) 2 , especially preferably -SO 3 M or -COOM, most preferably -COOM.

[0146] M is H, metal atom, NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

[0147] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred.

[0148] As M, -H, a metal atom or -NR 7 4 , more preferably -H, alkali metal (Group 1), alkaline earth metal (Group 2) or -NR 7 4 , further preferably -H, -Na, -K, -Li or NH 4 , and more preferably -H, -Na, -K or NH 4 , particularly preferably -H, -Na or NH 4 , most preferably -H or -NH 4 .

[0149] In the dimer and trimer of the monomer (I), the polymerized units (I) may have different anionic groups or may have the same anionic groups.

[0150] In the polymer (I), each polymerized unit (I) may have a different anionic group or may have the same anionic group.

[0151] The monomer (I) is also preferably a monomer represented by the general formula (Ia).

[0152] The polymer (I) is also preferably a polymer comprising a polymerized unit (Ia) based on a monomer represented by the general formula (Ia).

[0153] CF 2 =CF-O-Rf 0 -A 0 (Ia)

[0154] (In the formula, A 0 is an anionic group, Rf 0 It is perfluorinated and may be chain or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and is a perfluorinated divalent linking group that optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen.

[0155] The monomer (I) is also preferably a monomer represented by the general formula (Ib).

[0156] The polymer (I) is also preferably a polymer comprising a polymerized unit (Ib) based on a monomer represented by the general formula (Ib).

[0157] CH 2 =CH-O-Rf 0 -A 0 (Ib)

[0158] (In the formula, A 0 is an anionic group, Rf 0 is a perfluorinated divalent linking group as defined in Formula Ia.

[0159] In the general formula (I), A 0 A sulfate ester group is one of the preferred forms. 0 For example, -CH 2 OSO 3 M, -CH 2 CH 2 OSO 3 M or -SO 2 NR'CH 2 CH 2 OSO 3 M, wherein R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as described above.

[0160] A 0 In the case of a sulfate ester group, examples of the monomer represented by the general formula (I) include CF 2 =CF(OCF 2 CF 2 CH 2 OSO3 M), CH 2 =CH((CF 2 ) 4 CH 2 OSO 3 M), CF 2 =CF(O(CF 2 ) 4 CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CH 2 OSO 3 M), CH 2 =CH((CF 2 ) 4 CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OSO 3 M), CH 2 =CH(CF 2 CF 2 CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF 2 CF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OSO 3 M), CH 2 =CH(CF 2 CF 2 CF 2 CH 2 OSO 3 M), etc. In the above formula, M is the same as above.

[0161] In general formula (I), A0 A sulfonate group is also one of the preferred embodiments. 0 , for example -SO 3 M, where M is the same as above.

[0162] A 0 In the case of a sulfonate group, examples of the monomer represented by the general formula (I) include CF 2 =CF(OCF 2 CF 2 SO 3 M), CF 2 =CF(O(CF 2 ) 3 SO 3 M), CF 2 =CF(O(CF 2 ) 4 SO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )SO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 SO 3 M), CH 2 =CH(CF 2 CF 2 SO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CF 2 CF 2 SO 3 M), CH 2 =CH((CF 2 ) 4 SO 3 M), CH 2 =CH((CF 2 ) 3 SO 3 M) etc. In the above formula, M is the same as above.

[0163] In the general formula (I), A 0 A carboxylic acid ester group is also one of the preferred embodiments. 0 , such as COOM or SO 2 NR'CH 2COOM, wherein R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above. 0 In the case of a carboxylate group, examples of the monomer represented by the general formula (I) include CF 2 =CF(OCF 2 CF 2 COOM), CF 2 =CF(O(CF 2 ) 3 COOM), CF 2 =CF(O(CF 2 ) 5 COOM), CF 2 =CF(OCF 2 CF(CF 3 )COOM)、CF 2 =CF(OCF 2 CF(CF 3 )O(CF 2 ) n COOM)(n greater than 1), CH 2 =CH(CF 2 CF 2 COOM), CH 2 =CH((CF 2 ) 4 COOM), CH 2 =CH((CF 2 ) 3 COOM), CF 2 =CF(OCF 2 CF 2 SO 2 NR'CH 2 COOM), CF 2 =CF(O(CF 2 ) 4 SO 2 NR'CH 2 COOM), CF 2 =CF(OCF 2 CF(CF 3 )SO 2 NR'CH 2 COOM), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 NR'CH 2 COOM), CH 2 =CH(CF 2 CF2 SO 2 NR'CH 2 COOM), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CF 2 CF 2 SO 2 NR'CH 2 COOM)、CH 2 =CH((CF 2 ) 4 SO 2 NR'CH 2 COOM)、CH 2 =CH((CF 2 ) 3 SO 2 NR'CH 2 In the above formula, R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0164] In the general formula (I), A 0 A phosphate group is also one of the preferred embodiments. 0 , for example -CH 2 OP(O)(OM) 2 、[-CH 2 O] 2 P(O)(OM), -CH 2 CH 2 OP(O)(OM) 2 、[-CH 2 CH 2 O] 2 P(O)(OM),[-SO 2 NR'CH 2 CH 2 O] 2 P(O)(OM) or SO 2 NR'CH 2 CH 2 OP(O)(OM) 2 , wherein R' is an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0165] In A 0 In the case of a phosphate ester, examples of the monomer represented by the general formula (I) include CF 2 =CF(OCF 2 CF 2 CH 2 OP(O)(OM)2 ), CF 2 =CF(O(CF 2 ) 4 CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF 2 CF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OP(O)(OM) 2 ), CH 2 =CH(CF 2 CF 2 CH 2 OP(O)(OM) 2 ), CH 2 =CH((CF 2 ) 4 CH 2 OP(O)(OM) 2 ), CH 2 =CH((CF 2 ) 3 CH 2 OP(O)(OM) 2 ) etc. In the above formula, M is the same as above.

[0166] In the general formula (I), A 0 It is also one of the preferred forms to be a phosphonate group. 0When the phosphonate group is, the monomer represented by the general formula (I) includes CF 2 =CF(OCF 2 CF 2 P(O)(OM) 2 ), CF 2 =CF(O(CF 2 ) 4 P(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )P(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 P(O)(OM) 2 ), CH 2 =CH(CF 2 CF 2 P(O)(OM) 2 ), CH 2 =CH((CF 2 ) 4 P(O)(OM) 2 ), CH 2 =CH((CF 2 ) 3 P(O)(OM) 2 ), where M is the same as above.

[0167] The monomer (I) is preferably a monomer (1) represented by the general formula (1).

[0168] The polymer (I) is preferably a polymer (1) comprising a polymerized unit (1) based on a monomer represented by the general formula (1).

[0169] CX 2 =CY(-CZ 2 -O-Rf-A) (1)

[0170] (wherein, X is the same or different and is -H or F, Y is -H, -F, alkyl or fluorinated alkyl, and Z is the same or different and is -H, -F, alkyl or fluorinated alkyl. 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 74 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group). wherein at least one of X, Y and Z contains a fluorine atom.

[0171] In the production method of the present invention, the monomer (1) represented by the general formula (1) may be copolymerized with other monomers.

[0172] The polymer (1) may be a homopolymer of the fluoroallyl ether compound represented by the general formula (1), or may be a copolymer with other monomers.

[0173] The fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms is an alkylene group having no structure with an oxygen atom at the end and having an ether bond between carbon atoms.

[0174] In the general formula (1), X is -H or F. Both X may be -F, or at least one of them may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0175] In the general formula (1), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group not containing fluorine atoms and has at least 1 carbon atom. The alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and further preferably 3 or less carbon atoms. The fluorine-containing alkyl group is an alkyl group containing at least 1 fluorine atom and has at least 1 carbon atom. The fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and further preferably 3 or less carbon atoms. As the above-mentioned Y, -H, -F or -CF 3 , more preferably -F.

[0176] In the general formula (1), Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. The above-mentioned alkyl group is an alkyl group not containing fluorine atoms and has a carbon number of 1 or more. The carbon number of the above-mentioned alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above-mentioned fluorinated alkyl group is an alkyl group containing at least 1 fluorine atom and has a carbon number of 1 or more. The carbon number of the above-mentioned fluorinated alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. As the above-mentioned Z, -H, -F or -CF 3 , more preferably -F.

[0177] In the general formula (1), at least one of X, Y and Z contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0178] In the general formula (1), 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.

[0179] The number of carbon atoms in the fluorinated alkylene group is preferably 2 or more. In addition, the number of carbon atoms in the fluorinated alkylene group is preferably 30 or less, more preferably 20 or less, further preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. Examples of the fluorinated alkylene group include -CF 2 -、-CH 2 CF 2 -、-CF 2 CF 2 -、-CF 2 CH 2 -、-CF 2 CF 2 CF 2 -、-CF 2 CF 2 CH 2 -、-CF(CF 3 )-、-CF(CF 3 )CF 2 -、-CF(CF 3 )CH 2 - etc. The above-mentioned fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0180] The number of carbon atoms in the fluorinated alkylene group having an ether bond is preferably 3 or more. In addition, the number of carbon atoms in the fluorinated alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, further preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorinated alkylene group having an ether bond is also preferably, for example, of the general formula:

[0181] [Chemistry 1]

[0182]

[0183] (Where Z 1 F or CF 3 ; Z 2 and Z 3 H or F; Z 4 H, F or CF 3 ; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0184] Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF 3 )CF 2 -O-CF(CF 3 )-、-(CF(CF 3 )CF 2 -O) n -CF(CF 3)-(wherein n is an integer from 1 to 10), -CF(CF 3 )CF 2 -O-CF(CF 3 )CH 2 -、-(CF(CF 3 )CF 2 -O) n -CF(CF 3 )CH 2 -(wherein n is an integer from 1 to 10), -CH 2 CF 2 CF 2 O-CH 2 CF 2 CH 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 CH 2 -、-CF 2 CF 2 O-CF 2 -、-CF 2 CF 2 O-CF 2 CH 2 - etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0185] In the general formula (1), A is -COOM, -SO 3 M, -OSO 3 M or -C(CF 3 ) 2 OM (M is H, metal atom, NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0186] As R 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 of alkyl.

[0187] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0188] As M, H, a metal atom or NR 7 4 , more preferably H, alkali metals (Group 1), alkaline earth metals (Group 2) or NR 7 4 , more preferably H, Na, K, Li or NH 4 , and more preferably H, Na, K or NH 4 , particularly preferably H, Na or NH 4 , most preferably H or NH 4 .

[0189] As A, -COOM or -SO is preferred 3 M is more preferably -COOM.

[0190] Examples of the monomer represented by the general formula (1) include the general formula (1a):

[0191] CX 2 =CFCF 2 -O-(CF(CF 3 )CF 2 O) n5 -CF(CF 3 )-A(1a)

[0192] The fluoroallyl ether compound represented by (wherein, each X is the same and represents F or H. n5 represents 0 or an integer from 1 to 10, and A has the same meaning as defined above) is preferred.

[0193] In the general formula (1a), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, from the viewpoint of obtaining particles having a small primary particle size.

[0194] In the production method of the present invention, the monomer represented by the general formula (1a) may be copolymerized with other monomers.

[0195] The polymer (1) may be a homopolymer of the fluoroallyl ether compound represented by the general formula (1a), or may be a copolymer with other monomers.

[0196] The monomer (1) is preferably a monomer represented by the general formula (1A).

[0197] The polymerized unit (1) is preferably a polymerized unit (1A) based on a monomer represented by the general formula (1A).

[0198] CH 2 =CF(-CF 2 -O-Rf-A)(1A)

[0199] (Wherein, Rf and A are the same as above.)

[0200] In the production method of the present invention, the monomer represented by the general formula (1A) may be copolymerized with other monomers.

[0201] The polymer (1) may be a homopolymer of the monomer represented by the general formula (1A) or a copolymer with other monomers.

[0202] Specific examples of the monomer represented by formula (1A) include monomers of the general formula

[0203] [Chemistry 2]

[0204]

[0205] (Where Z 1 F or CF 3 ; Z 2 and Z 3 H or F; Z 4 H, F or CF 3 ; p1+q1+r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, wherein Z 3 and Z 4 When all are H, p1+q1+r1+s1 is not 0; A is the same as defined above). More specifically, preferably,

[0206] [Chemistry 3]

[0207]

[0208] CH 2 =CFCF 2 OCH 2 CF 2 -A, CH 2 =CFCF 2 O(CH 2 CF 2 CF 2 O)CH 2 CF 2 -A,

[0209] CH 2 =CFCF 2 OCH 2 CF 2 CH 2 -A,

[0210] CH 2 =CFCF 2 O(CH 2 CF 2 CF 2 O)CH 2 CF2 CH 2 -A,

[0211] CH 2 =CFCF 2 OCF 2 CF 2 -A, CH 2 =CFCF 2 O(CF 2 CF 2 CF 2 O)CF 2 CF 2 -A, CH 2 =CFCF 2 OCF 2 CF 2 CH 2 -A,

[0212] CH 2 =CFCF 2 O(CF 2 CF 2 CF 2 O)CF 2 CF 2 CH 2 -A,

[0213] CH 2 =CFCF 2 OCF 2 -A, CH 2 =CFCF 2 O(CF 2 CF 2 O(CF 2 -A,

[0214] CH 2 =CFCF 2 OCF 2 CH 2 -A,

[0215] CH 2 =CFCF 2 O(CF 2 CF 2 O)CF 2 CH 2 -A, etc.,

[0216] Among them, preferably

[0217] [Chemical Formula 4]

[0218]

[0219] As the monomer represented by the general formula (1A), A in the formula (1A) is preferably -COOM, and is particularly preferably selected from CH 2 =CFCF 2 OCF(CF 3 )COOM and CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )COOM (wherein M is the same as defined above), more preferably CH 2 =CFCF 2 OCF(CF 3 )COOM.

[0220] In addition, examples of the monomer represented by the general formula (1) include monomers represented by the following formulas.

[0221] CF 2 =CFCF 2 -O-Rf-A

[0222] (Wherein, Rf and A are the same as above.)

[0223] More specifically, we can cite

[0224] [Chemistry 5]

[0225] CF 2 =CFCF 2 OCF 2 CF 2 CF 2 -A,

[0226]

[0227] CF 2 =CFCF 2 OCF 2 CF 2 CF 2 CH 2 -A

[0228] wait.

[0229] The monomer (I) is also preferably a monomer (2) represented by the general formula (2).

[0230] The polymer (I) is also preferably a polymer (2) comprising a polymerized unit (2) based on a monomer represented by the general formula (2).

[0231] CX2=CY(-O-Rf-A) (2)

[0232] (In the formula, X is the same or different and is -H or F, 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 having an ether bond or a keto group. A is the same as above.)

[0233] In the production method of the present invention, the monomer (2) represented by the general formula (2) may be copolymerized with other monomers.

[0234] The polymer (2) may be a homopolymer of the monomer represented by the general formula (2), or a copolymer with other monomers.

[0235] In the general formula (2), X is -H or F. Both Xs may be -F, or at least one of them may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0236] In the general formula (2), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain fluorine atoms and has at least 1 carbon atom. The carbon number of the above alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The fluorine-containing alkyl group is an alkyl group that contains at least 1 fluorine atom and has at least 1 carbon atom. The carbon number of the above fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. As Y, -H, -F or CF is preferred. 3 , more preferably -F.

[0237] In the general formula (2), at least one of X and Y preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0238] In the 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 having an ether bond, or a fluorinated alkylene group having 2 to 100 carbon atoms and having a keto group. It should be noted that the fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond is an alkylene group having an ether bond between carbon atoms and not having an oxygen atom at the end.

[0239] The number of carbon atoms of the fluorinated alkylene group of Rf is preferably 2 or more. In addition, it is preferably 30 or less, more preferably 20 or less, further preferably 10 or less, and particularly preferably 5 or less. Examples of the fluorinated alkylene group include -CF 2 -、-CH 2 CF 2 -、-CF 2 CF 2 -、-CF 2 CH 2 -、-CF 2 CF 2 CH 2 -、-CF(CF3 )-、-CF(CF 3 )CF 2 -、-CF(CF 3 )CH 2 -、-CF 2 CF 2 CF 2 -、CF 2 CF 2 CF 2 CF 2 - etc. The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0240] The number of carbon atoms in the fluorinated alkylene group having an ether bond is preferably 3 or more. In addition, the number of carbon atoms in the fluorinated alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, further preferably 12 or less, and particularly preferably 5 or less. The fluorinated alkylene group having an ether bond is preferably, for example, of the general formula:

[0241] [Chemistry 6]

[0242]

[0243] (Where Z 1 F or CF 3 ; Z 2 and Z 3 H or F; Z 4 H, F or CF 3 ; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0244] Specific examples of the fluorinated alkylene group having an ether bond include -CF 2 CF(CF 3 )OCF 2 CF 2 -、-CF(CF 3 )CF 2 -O-CF(CF 3 )-、-(CF(CF 3 )CF 2 -O) n -CF(CF 3 )-(wherein n is an integer from 1 to 10), -CF(CF 3 )CF 2 -O-CF(CF 3 )CH 2 -、-(CF(CF 3 )CF 2 -O) n -CF(CF3 )CH 2 -(wherein n is an integer from 1 to 10), -CH 2 CF 2 CF 2 O-CH 2 CF 2 CH 2 -、-CF 2 CF 2 CF 2 O-CF 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 CF 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 CH 2 -、-CF 2 CF 2 O-CF 2 -、-CF 2 CF 2 O-CF 2 CH 2 - etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0245] The carbon number of the fluorinated alkylene group having a keto group is preferably 3 or more. The carbon number of the fluorinated alkylene group having a keto group is preferably 60 or less, more preferably 30 or less, further preferably 12 or less, particularly preferably 5 or less.

[0246] Specific examples of the fluorinated alkylene group having a keto group include -CF 2 CF(CF 3 )CO-CF 2 -、-CF 2 CF(CF 3 )CO-CF 2 CF 2 -、-CF 2 CF(CF 3 )CO-CF 2 CF 2 CF 2 -、-CF 2 CF(CF3 )CO-CF 2 CF 2 CF 2 CF 2 - etc. The fluorine-containing alkylene group having a keto group is preferably a perfluoroalkylene group.

[0247] The monomer represented by the general formula (2) is preferably at least one selected from the group consisting of monomers represented by the general formulae (2a), (2b), (2c), (2d) and (2e).

[0248] CF 2 =CF-O-(CF 2 ) n1 -A(2a)

[0249] (In the formula, n1 represents an integer of 1 to 10, and A is the same as above.)

[0250] CF 2 =CF-O-(CF 2 C(CF 3 )F) n2 -A(2b)

[0251] (In the formula, n2 represents an integer of 1 to 5, and A has the same definition as above.)

[0252] CF 2 =CF-O-(CFX 1 ) n3 -A(2c)

[0253] (Where X 1 Indicates F or CF 3 , n3 represents an integer from 1 to 10, and A has the same definition as above. )

[0254] CF 2 =CF-O-(CF 2 CFX 1 O) n4 -(CF 2 ) n6 -A(2d)

[0255] (wherein, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, A and X 1 Same as the above definition.)

[0256] CF 2 =CF-O-(CF 2 CF 2 CFX 1 O) n5 -CF 2 CF 2 CF 2-A(2e)

[0257] (where n5 represents an integer from 0 to 10, A and X 1 Same as the above definition.)

[0258] In the general formula (2a), the above n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.

[0259] Examples of the monomer represented by the general formula (2a) include CF 2 =CF-O-CF 2 COOM, CF 2 =CF(OCF 2 CF 2 COOM), CF 2 =CF(O(CF 2 ) 3 COOM), CF 2 =CF(OCF 2 CF 2 SO 3 M) (wherein, M has the same definition as above).

[0260] In the general formula (2b), n2 is preferably an integer of 3 or less from the viewpoint of dispersion stability of the obtained composition.

[0261] In the general formula (2c), from the viewpoint of water solubility, n3 is preferably an integer of 5 or less, the above-mentioned A is preferably -COOM, and the above-mentioned M is preferably H or NH 4 .

[0262] In the general formula (2d), from the viewpoint of dispersion stability of the composition, X 1 Preferably -CF 3 From the perspective of water solubility, n4 is preferably an integer of 5 or less, A is preferably -COOM, and M is preferably H or NH 4 .

[0263] Examples of the monomer represented by the general formula (2d) include CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 COOM, CF 2 =CFOCF 2 CF(CF 3 )OCF 2 COOM, CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2CF 2 COOM (where M represents H, NH 4 or alkali metals).

[0264] In the general formula (2e), from the viewpoint of water solubility, n5 is preferably an integer of 5 or less, A is preferably -COOM, and M is preferably H or NH 4 .

[0265] Examples of the monomer represented by the general formula (2e) include CF 2 =CFOCF 2 CF 2 CF 2 COOM (where M represents H, NH 4 or alkali metals).

[0266] The monomer (I) is also preferably a monomer (3) represented by the general formula (3).

[0267] The polymer (I) is also preferably a polymer (3) comprising a polymerized unit (3) based on a monomer represented by the general formula (3).

[0268] CX 2 =CY(-Rf-A) (3)

[0269] (In the formula, X is the same or different and is -H or F, 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 an ether bond having 2 to 100 carbon atoms. A is the same as above.)

[0270] In the production method of the present invention, the monomer (3) represented by the general formula (3) may be copolymerized with other monomers.

[0271] The polymer (3) may be a homopolymer of the monomer represented by the general formula (3), or a copolymer with other monomers.

[0272] The fluorine-containing alkylene group having an ether bond and having 2 to 100 carbon atoms is an alkylene group having no structure with an oxygen atom at the end and having an ether bond between carbon atoms.

[0273] In the general formula (3), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In the general formula (3), at least one of X and Y preferably contains a fluorine atom.

[0274] The monomer represented by general formula (3) is preferably selected from general formula (3a):

[0275] CF 2 =CF-(CF 2 ) n1 -A(3a)

[0276] (wherein n1 represents an integer of 1 to 10, and A has the same meaning as defined above) and the general formula (3b):

[0277] CF 2 =CF-(CF 2 C(CF 3 )F) n2 -A(3b)

[0278] (wherein n2 represents an integer of 1 to 5, and A has the same meaning as defined above) is at least one member selected from the group consisting of monomers represented by the formula (wherein n2 represents an integer of 1 to 5, and A has the same meaning as defined above).

[0279] In the general formula (3a) and the general formula (3b), A is preferably -SO 3 M or COOM, M is preferably H, metal atom, NR 7 4 , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 7 represents H or an organic group.

[0280] 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 NH 4 .

[0281] Examples of the monomer represented by the general formula (3a) include CF 2 =CFCF 2 COOM (wherein M has the same definition as above).

[0282] In the general formula (3b), from the viewpoint of dispersion stability of the obtained composition, n2 is preferably an integer of 3 or less, A is preferably -COOM, and M is preferably H or NH 4 .

[0283] Next, a preferred configuration when m is an integer of 2 or more in the general formula (I) will be described.

[0284] 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).

[0285] The polymer (I) is also preferably a polymer (4) comprising a polymerized unit (4) based on at least one monomer selected from the group consisting of monomers represented by the general formula (4a) and the general formula (4b).

[0286] CF 2 =CF-CF 2 -OQ F1 -CF(-Q F2 -CZ 1 Z2 -A) 2 (4a)

[0287] (Where Z 1 , Z 2 and A are the same as above, Q F1 and Q F2 The same or different, a single bond, a fluorinated alkylene group containing or not containing an ether bond between carbon and carbon, or a fluorinated oxyalkylene group containing or not containing an ether bond between carbon and carbon.

[0288] CF 2 =CF-OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A) 2 (4b)

[0289] (Where Z 1 , Z 2 , A, Q F1 and Q F2 Same as the above definition.)

[0290] Examples of the monomers represented by the general formula (4a) and the general formula (4b) include:

[0291] [Chemistry 7]

[0292] wait.

[0293] The monomer (I) is preferably at least one selected from the group consisting of the monomer (1), the monomer (2) and the monomer (3), more preferably the monomer (1), and further preferably the monomer (1A).

[0294] The polymer (I) is preferably at least one selected from the group consisting of the polymer (1), the polymer (2) and the polymer (3), and more preferably the polymer (1).

[0295] In the production method of the present invention, the monomer (I) may be copolymerized with other monomers.

[0296] The polymer (I) may be a homopolymer consisting only of the polymerized unit (I), or may be a copolymer comprising the polymerized unit (I) and a polymerized unit based on other monomers copolymerizable with the monomer represented by the general formula (I). From the aspect of solubility in an aqueous medium, a homopolymer consisting only of the polymerized unit (I) is preferred. The polymerized unit (I) may be the same or different each time it appears, and the polymer (I) may contain polymerized units (I) based on two or more different monomers represented by the general formula (I).

[0297] As the above other monomer, preferably: 2(wherein R is independently H, F or a perfluoroalkyl group having 1 to 4 carbon atoms). In addition, as other monomers, fluorine-containing ethylenic monomers having 2 or 3 carbon atoms are preferred. As other monomers, for example, CF 2 =CF 2 CF 2 =CFCl, CH 2 =CF 2 CFH=CH 2 CFH=CF 2 CF 2 =CFCF 3 , CH 2 =CFCF 3 , CH 2 =CHCF 3 、CHF=CHCF 3 (E body), CHF=CHCF 3 (Z body) etc.

[0298] Among them, tetrafluoroethylene (CF 2 =CF 2 ), chlorotrifluoroethylene (CF 2 =CFCl) and vinylidene fluoride (CH 2 =CF 2 ), more preferably tetrafluoroethylene. 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 each time they appear, and polymer (I) may contain polymerization units based on two or more different other monomers.

[0299] In addition, examples of the other monomers include general formula (n1-2):

[0300] [Chemistry 8]

[0301]

[0302] (Where X 1 , X 2 Same or different, H or F; X 3 H, F, Cl, CH 3 or CF 3 ;X 4 , X 5 are the same or different, and are H or F; a and c are the same or different, and are 0 or 1. 3 The monomer is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond having 2 to 100 carbon atoms).

[0303] Specifically, CH 2 =CFCF 2 -O-Rf 3 CF 2 =CF-O-Rf 3 CF 2 =CFCF 2 -O-Rf 3 CF 2 =CF-Rf 3 , CH 2 =CH-Rf 3 , CH 2 =CH-O-Rf 3 (Where Rf 3 Same as the above formula (n1-2)) etc.

[0304] As the other monomers, the following may also be mentioned:

[0305] [Chemistry 9]

[0306]

[0307] (Where X 9 H, F or CH 3 ; Rf 4 is a fluorinated acrylate monomer represented by a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond having 2 to 100 carbon atoms. 4 The basis can be cited

[0308] [Chemistry 10]

[0309]

[0310] (Where Z 8 is H, F or Cl; d1 is an integer from 1 to 4; e1 is an integer from 1 to 10),

[0311] -CH(CF 3 ) 2 ,

[0312]

[0313] (wherein e2 is an integer from 1 to 5),

[0314]

[0315] (wherein, d3 is an integer from 1 to 4; e3 is an integer from 1 to 10), etc.

[0316] As the other monomers, the formula (n2-2) may also be mentioned:

[0317] CH 2 =CHO-Rf 5 (n2-2)

[0318] (Where Rf 5 The fluorine-containing vinyl ether is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.

[0319] Specifically, preferred examples of the monomer of the general formula (n2-2) include

[0320] [Chemistry 11]

[0321]

[0322] (Where Z 9 is H or F; e4 is an integer from 1 to 10),

[0323]

[0324] (wherein e5 is an integer from 1 to 10),

[0325]

[0326] (wherein e6 is an integer from 1 to 10) etc.

[0327] More specifically, we can cite

[0328] [Chemistry 12]

[0329] CH 2 =CHOCH 2 CF 2 CF 2 H.

[0330]

[0331] CH 2 =CHOCH 2 CF 2 CF 3 ,

[0332] CH 2 =CHOCH 2 CF 3 ,

[0333] wait.

[0334] In addition, the general formula (n2-3) can also be cited:

[0335] CH 2 =CHCH 2O-Rf 6 (n2-3)

[0336] (Where Rf 6 is a fluorinated allyl ether represented by a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond having 2 to 100 carbon atoms, and the general formula (n2-4):

[0337] CH 2 =CH-Rf 7 (n2-4)

[0338] (Where Rf 7 The fluorine-containing vinyl monomer is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.

[0339] Specific examples of the monomers represented by the general formulae (n2-3) and (n2-4) include:

[0340] [Chemistry 13]

[0341] CH 2 =CHCH 2 OCH 2 CF 2 CF 2 H.

[0342]

[0343] CH 2 =CHCH 2 OCH 2 CF 2 CF 3 ,

[0344] CH 2 =CHCH 2 OCH 2 CF 3 ,

[0345] Etc. monomers.

[0346] The polymer (I) usually has an end group. The end group is an end group generated during polymerization, and a representative end group is independently selected from hydrogen, iodine, bromine, a linear or branched alkyl group, and a linear or branched fluoroalkyl group, and may arbitrarily contain at least one linear heteroatom. The number of carbon atoms in the alkyl group or the fluoroalkyl group is preferably 1 to 20. These end groups are usually generated by an initiator or chain transfer agent used in the formation of the polymer (I), or generated in a chain transfer reaction.

[0347] In the polymer (I), the content of the polymerized units (I) is preferably 1.0 mol% or more, 3.0 mol% or more, 5.0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, or 90 mol% or more relative to all the polymerized units. The content of the polymerized units (I) is particularly preferably substantially 100 mol%, and the polymer (I) is most preferably composed of the polymerized units (I) alone.

[0348] In polymer (I), the content of polymerized units based on other monomers copolymerizable with the monomer represented by general formula (I) is preferably 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less relative to all polymerized units. The content of polymerized units based on other monomers copolymerizable with the monomer represented by general formula (I) is particularly preferably substantially 0 mol%, and polymer (I) most preferably does not contain polymerized units based on other monomers.

[0349] The number average molecular weight of polymer (I) is preferably 0.1×10 4 More preferably, 0.2×10 4 More preferably, 0.3×10 4 More preferably, 0.4×10 4 More than 0.5×10 4 More than 1.0×10 4 Above, particularly preferably 3.0×10 4 More than, most preferably 3.1×10 4 In addition, it is preferably 75.0×10 4 Less than, more preferably 50.0×10 4 Below, more preferably 40.0×10 4 Below, especially preferably 30.0×10 4 Below, particularly preferably 20.0×10 4 The number average molecular weight and weight average molecular weight are values ​​of molecular weight calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. In addition, when it is impossible to measure by GPC, the number average molecular weight of polymer (I) can be obtained based on the correlation between the number average molecular weight calculated by the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured according to JIS K 7210.

[0350] The lower limit of the weight average molecular weight of the polymer (I) is preferably 0.2×10 4 Above, 0.4×10 4 Above, 0.6×10 4 Above, 0.8×10 4 Above, 1.0×10 4 Above, 2.0×10 4 Above, 5.0×10 4 Above, 10.0×10 4 Above, 15.0×10 4 Above, 20.0×10 4 Above, 25.0×10 4 The upper limit of the weight average molecular weight of the polymer (I) is preferably 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 the following.

[0351] The polymer (I) preferably has an ion exchange rate (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the polymer backbone relative to the ionic groups. 2 F) is not considered an ionic group for the purpose of determining IXR.

[0352] IXR is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and particularly preferably 8 or more. IXR is more preferably 43 or less, further preferably 33 or less, and particularly preferably 23 or less.

[0353] The ion exchange capacity of polymer (I) is preferably 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, and 3.50 meq / g or more. The ion exchange capacity is the content of the ionic group (anionic group) of polymer (I), and is calculated from the composition of polymer (I).

[0354] In the polymer (I), the ionic groups (anionic groups) are typically distributed along the polymer main chain. The polymer (I) preferably comprises a polymer main chain and repeating side chains bonded to the main chain, and the side chains preferably have ionic groups.

[0355] The polymer (I) preferably comprises an ionic group having a pKa of less than 10, more preferably less than 7. The ionic group of the polymer (I) is preferably selected from the group consisting of sulfonates, carboxylates, phosphonates and phosphates.

[0356] The terms "sulfonate, carboxylate, phosphonate and phosphate" refer to the respective salt or the respective acid capable of forming a salt. In case a salt is used, it is preferably an alkali metal salt or an ammonium salt. The preferred ionic group is a sulfonate group.

[0357] The polymer (I) is preferably water-soluble. Water-solubility refers to the property of being easily dissolved or dispersed in an aqueous medium. For example, the particle size of a water-soluble polymer (I) cannot be measured by dynamic light scattering (DLS). On the other hand, the particle size of a water-insoluble polymer (I) can be measured by dynamic light scattering (DLS).

[0358] A polymer (11) can also be used as the polymer (I), wherein the polymer (11) is a polymer (11) of a monomer (11) represented by the general formula (11), wherein the content of the polymerized units (11) based on the monomer (11) is 50 mol% or more relative to the total polymerized units constituting the polymer (11), and the weight average molecular weight (Mw) is 38.0×10 4 The polymer (11) is a novel polymer.

[0359] General formula (11): CX 2 =CY-CF 2 -O-Rf-A

[0360] (wherein X and Y are independently H, F, CH 3 or CF 3 , at least one of X and Y is F. Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having an ether bond having 2 to 100 carbon atoms. A is -COOM, -SO 3 M, -OSO 3 M or -C(CF 3 ) 2 OM (M is H, metal atom, NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0361] In the general formula (11), X and Y are independently H, F, CH 3 or CF 3, at least one of X and Y is F. X is preferably H or F, more preferably H. Y is preferably H or F, more preferably F.

[0362] Rf and A in the general formula (11) are the same as Rf and A in the general formula (1) representing the monomer constituting the polymer (1).

[0363] The polymer (11) may be a homopolymer consisting only of polymerized units (11) based on the monomer (11), or may be a copolymer comprising polymerized units (11) and polymerized units based on other monomers copolymerizable with the monomer (11). The other monomers are as described above. Each occurrence of the polymerized unit (11) may be the same or different, and the polymer (11) may contain polymerized units (11) based on two or more different monomers represented by the general formula (11).

[0364] The content of the polymerized units (11) in the polymer (11) is preferably 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 99 mol% or more, based on all the polymerized units constituting the polymer (11). The content of the polymerized units (11) is particularly preferably substantially 100 mol%, and the polymer (11) is most preferably composed of the polymerized units (11) alone.

[0365] In the polymer (11), the content of the polymerized units based on other monomers copolymerizable with the monomer (11) is preferably 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, and 50 mol% or less, relative to all the polymerized units constituting the polymer (11). The content of the polymerized units based on other monomers copolymerizable with the monomer (11) is particularly preferably substantially 0 mol%, and the polymer (11) most preferably contains no polymerized units based on other monomers.

[0366] The lower limit of the weight average molecular weight of the polymer (11) is preferably 38.0×10 4 Above, 40.0×10 4 The upper limit of the weight average molecular weight of the polymer (11) is preferably 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 the following.

[0367] The lower limit of the number average molecular weight of the polymer (11) is preferably 5.0×10 4 8.0×10 4 , 10.0×104 Above, 12.0×10 4 The upper limit of the number average molecular weight of the polymer (11) is preferably 75.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 Below, 30.0×10 4 the following.

[0368] A polymer (12) can also be used as the polymer (I). The polymer (12) is a polymer (12) of a monomer (12) represented by the general formula (12), wherein the content of the polymerized units (12) based on the monomer (12) is 50 mol% or more relative to the total polymerized units constituting the polymer (12), and the weight average molecular weight (Mw) is 1.4×10 4 The polymer (12) is a novel polymer.

[0369] General formula (12): CX 2 =CX-O-Rf-A

[0370] (wherein X is independently F or CF 3 , 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 or a keto group. A is -COOM, -SO 3 M, -OSO 3 M or -C(CF 3 ) 2 OM (M is -H, metal atom, -NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0371] In the general formula (12), X is independently F or CF 3 It is preferred that at least one X is F, and it is more preferred that all X are F.

[0372] Rf and A in the general formula (12) are the same as Rf and A in the general formula (2) representing the monomer constituting the polymer (2).

[0373] The polymer (12) may be a homopolymer consisting only of polymerized units (12) based on the monomer (12), or a copolymer comprising polymerized units (12) and polymerized units based on other monomers copolymerizable with the monomer (12). The other monomers are as described above. Each occurrence of the polymerized unit (12) may be the same or different, and the polymer (12) may contain polymerized units (12) based on two or more different monomers represented by the general formula (12).

[0374] The content of the polymerized units (12) in the polymer (12) is preferably 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 99 mol% or more, relative to all the polymerized units constituting the polymer (12). The content of the polymerized units (12) is particularly preferably substantially 100 mol%, and the polymer (12) is most preferably composed only of the polymerized units (12).

[0375] In the polymer (12), the content of polymerized units based on other monomers copolymerizable with the monomer (12) is preferably 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, and 1 mol% or less, relative to all polymerized units constituting the polymer (12). The content of polymerized units based on other monomers copolymerizable with the monomer (12) is particularly preferably substantially 0 mol%, and the polymer (12) most preferably does not contain polymerized units based on other monomers.

[0376] The lower limit of the weight average molecular weight (Mw) of the polymer (12) is preferably 1.4×10 4 Above, 1.7×10 4 Above, 1.9×10 4 Above, 2.1×10 4 Above, 2.3×10 4 Above, 2.7×10 4 Above, 3.1×10 4 Above, 3.5×10 4 Above, 3.9×10 4 Above, 4.3×10 4 Above, 4.7×10 4 Above, 5.1×10 4 The upper limit of the weight average molecular weight (Mw) of the polymer (12) is preferably 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 the following.

[0377] The lower limit of the number average molecular weight (Mn) of the polymer (12) is preferably 0.7×10 4 Above, 0.9×10 4 Above, 1.0×10 4 Above, 1.2×10 4 Above, 1.4×10 4 Above, 1.6×10 4 Above, 1.8×10 4 The upper limit of the number average molecular weight (Mn) of the polymer (12) is preferably 75.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 Below, 30.0×10 4 Below, 20.0×10 4 the following.

[0378] The molecular weight distribution (Mw / Mn) of the polymer (12) is preferably 3.0 or less, more preferably 2.4 or less, further preferably 2.2 or less, particularly preferably 2.0 or less, and most preferably 1.9 or less.

[0379] The manufacturing method of the present invention comprises:

[0380] A step of polymerizing the monomer (I) represented by the general formula (I) in an aqueous medium in the substantial absence of a fluorinated surfactant (excluding the monomer (I) represented by the general formula (I)) to obtain a crude composition containing a polymer of the monomer (I); and

[0381] A step of removing dimers and trimers of the monomer (I) contained in the crude composition from the crude composition to obtain a polymer (I) having a content of dimers and trimers of the monomer (I) of 1.0 mass % or less based on the polymer (I).

[0382] In the present invention, "under the condition that there is substantially no fluorinated surfactant" means that the amount of the fluorinated surfactant relative to the aqueous medium is 10 mass ppm or less. The amount of the fluorinated surfactant relative to the aqueous medium is preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and even more preferably 1 mass ppb or less.

[0383] The fluorinated surfactant will be described later in the description of the polymerization of the fluorinated monomer.

[0384] The polymerization of the monomer (I) can be carried out by a known method. By producing a crude composition by such a method, a crude composition in which the polymer (I) is dispersed or dissolved in an aqueous medium can be obtained.

[0385] The polymer (11) in the polymer (I) is a new type of polymer and can be produced by the following production method (11): a production method for a polymer (11) of a monomer (11) by polymerizing a monomer (11) represented by the general formula (11) in an aqueous medium, wherein the oxygen concentration in the polymerization reaction system is maintained below 500 volume ppm.

[0386] In the production method (11), the oxygen concentration in the polymerization reaction system is 500 volume ppm or less. In the production method (11), the oxygen concentration in the reaction system is maintained at 500 volume ppm or less during the entire polymerization period of the monomer (11). The oxygen concentration in the reaction system is preferably 350 volume ppm or less, more preferably 300 volume ppm or less, further preferably 100 volume ppm or less, and particularly preferably 50 volume ppm or less. In addition, the oxygen concentration in the reaction system is usually 0.01 volume ppm or more.

[0387] In the production method (11), from the perspective of being able to easily produce a polymer (11) with a higher molecular weight, the polymerization temperature of the monomer (11) is preferably below 59°C, more preferably below 57°C, further preferably below 55°C, and particularly preferably below 53°C, and is preferably above 20°C, more preferably above 25°C, further preferably above 30°C, and particularly preferably above 35°C.

[0388] In the production method (11), the monomer (11) and the above-mentioned other monomers may be copolymerized.

[0389] In the production method (11), the polymerization pressure is usually atmospheric pressure to 10 MPaG. The polymerization pressure is appropriately determined depending on the type of monomers used, the molecular weight of the target polymer, and the reaction rate.

[0390] In the production method (11), the polymerization time is usually 1 to 200 hours, and may be 5 to 100 hours.

[0391] The polymer (12) in the polymer (I) is a new type of polymer and can be produced by the following production method (12): a production method for a polymer (12) of a monomer (12) by polymerizing a monomer (12) represented by the general formula (12) in an aqueous medium, wherein the oxygen concentration in the polymerization reaction system is maintained below 1500 volume ppm.

[0392] In the production method (12), the oxygen concentration in the polymerization reaction system is 1500 volume ppm or less. In the production method (12), the oxygen concentration in the reaction system is maintained at 1500 volume ppm or less during the entire polymerization period of the monomer (12). The oxygen concentration in the reaction system is preferably 500 volume ppm or less, more preferably 100 volume ppm or less, and further preferably 50 volume ppm or less. In addition, the oxygen concentration in the reaction system is usually 0.01 volume ppm or more.

[0393] In the production method (12), from the perspective of being able to easily produce a polymer (12) with a higher molecular weight, the polymerization temperature of the monomer (12) is preferably below 70°C, more preferably below 65°C, further preferably below 60°C, particularly preferably below 55°C, especially preferably below 50°C, particularly preferably below 45°C, most preferably below 40°C, preferably above 10°C, more preferably above 15°C, and further preferably above 20°C.

[0394] In the production method (12), the monomer (12) and the above-mentioned other monomers may be copolymerized.

[0395] In the production method (12), the polymerization pressure is usually atmospheric pressure to 10 MPaG. The polymerization pressure is appropriately determined depending on the type of monomers used, the molecular weight of the target polymer, and the reaction rate.

[0396] In the production method (12), the polymerization time is usually 1 to 200 hours, and may be 5 to 100 hours.

[0397] In the production method (11) and the production method (12), the oxygen concentration in the polymerization reaction system can be controlled by, for example, passing an inert gas such as nitrogen or argon, or, when a gaseous monomer is used, passing the gaseous monomer into the liquid phase or gas phase in the reactor. The oxygen concentration in the polymerization reaction system can be determined by measuring and analyzing the gas exhausted from the exhaust line of the polymerization system using a low-concentration oxygen analyzer.

[0398] In the production method (11) and the production method (12), the aqueous medium refers to a reaction medium for carrying out polymerization, and is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and a non-fluorinated organic solvent such as an alcohol, ether, or ketone and / or a fluorinated organic solvent having a boiling point of 40° C. or less. The aqueous medium is preferably water.

[0399] In the manufacturing method (11) and the manufacturing method (12), the polymerization of the monomer can be carried out in the presence of a polymerization initiator. The polymerization initiator is not particularly limited as long as it can generate free radicals in the above-mentioned polymerization temperature range, and a known oil-soluble and / or water-soluble polymerization initiator can be used. Furthermore, it is also possible to combine with a reducing agent and the like to initiate polymerization in a redox form. The concentration of the polymerization initiator is appropriately determined according to the type of monomer, the molecular weight of the target polymer, and the reaction rate.

[0400] As polymerization initiator, organic peroxides such as persulfate (for example ammonium persulfate), disuccinic acid peroxide, diglutaric acid peroxide can be used alone or in the form of these mixtures. In addition, it is also possible to share with reducing agents such as sodium sulfite to make a redox system for use. And then, in polymerization, free radical scavengers such as hydroquinone and catechol can also be added, or the decomposition agent of peroxides such as ammonium sulfite can be added to adjust the free radical concentration in the system.

[0401] As the polymerization initiator, persulfate is preferred because it can easily produce a polymer having a higher molecular weight. Examples of the persulfate include ammonium persulfate, potassium persulfate, sodium persulfate, and the like, and ammonium persulfate is preferred.

[0402] The amount of polymerization initiator added is not particularly limited, and may be added once, sequentially, or continuously at the initial stage of polymerization in an amount that does not significantly reduce the polymerization rate (e.g., a concentration of several ppm relative to water). The upper limit is a range in which the heat of polymerization reaction can be used to remove heat from the device surface and the reaction temperature can be increased, and a more preferred upper limit is a range in which the heat of polymerization reaction can be removed from the device surface.

[0403] In the production method (11) and the production method (12), a polymerization initiator may be added at the start of polymerization and also added during polymerization. The ratio of the amount of the polymerization initiator added at the start of polymerization to the amount of the polymerization initiator added during polymerization is preferably 95 / 5 to 5 / 95, more preferably 60 / 40 to 10 / 90, and further preferably 30 / 70 to 15 / 85. The method for adding the polymerization initiator added during polymerization is not particularly limited, and the entire amount may be added at once, may be added in two or more portions, or may be added continuously.

[0404] In the production method (11) and the production method (12), the total amount of the polymerization initiator used in the polymerization is preferably 0.00001% by mass to 10% by mass relative to the aqueous medium, from the viewpoint of being able to easily produce a polymer having a higher molecular weight. The total amount of the polymerization initiator used in the polymerization is more preferably 0.0001% by mass or more, further preferably 0.001% by mass or more, particularly preferably 0.01% by mass or more, more preferably 5% by mass or less, further preferably 2% by mass or less.

[0405] In the production method (11) and the production method (12), the total amount of the polymerization initiator used in the polymerization is preferably 0.001 mol% to 10 mol% relative to the monomer, from the viewpoint of being able to easily produce a fluorinated polymer having a higher molecular weight. The total amount of the polymerization initiator used in the polymerization is more preferably 0.005 mol% or more, further preferably 0.01 mol% or more, more preferably 5 mol% or less, further preferably 2.5 mol% or less, particularly preferably 2.2 mol% or less, and most preferably 2.0 mol% or less.

[0406] In the manufacturing method (11) and the manufacturing method (12), from the perspective of being able to easily manufacture a monomer with a higher molecular weight, the amount of the monomer containing the monomer (11) or the monomer (12) at the start of polymerization is preferably 30% by mass or more relative to the amount of the aqueous medium. As the amount of the monomer, it is more preferably 35% by mass or more, and further preferably 40% by mass or more. The upper limit of the amount of the monomer is not particularly limited, and from the perspective of making the polymerization proceed smoothly, it can be 200% by mass or less. The amount of the monomer at the start of polymerization refers to the total amount of the monomer (11) or the monomer (12) present in the reactor at the start of polymerization, and other monomers present.

[0407] In the production method (11) and the production method (12), the polymerization may be carried out in the presence of a pH adjuster. The pH adjuster may be added before the start of the polymerization or after the start of the polymerization.

[0408] As the pH adjuster, 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.

[0409] In the production method (11) and the production method (12), the polymerization of the monomer (11) or the monomer (12) can be carried out as follows: an aqueous medium, the monomer (11) or the monomer (12), and other monomers and other additives as needed are added to a reactor, the contents of the reactor are stirred, and the reactor is maintained at a predetermined polymerization temperature, and then a predetermined amount of a polymerization initiator is added to initiate a polymerization reaction, thereby carrying out the above-mentioned polymerization. After the polymerization reaction starts, monomers, polymerization initiators, and other additives can be added according to the purpose.

[0410] In the crude composition thus obtained, the polymer as the monomer (I) generally contains a total of more than 1.0% by mass of dimers and trimers relative to the mass of the polymer of the monomer (I). The content of dimers and trimers in the polymer as the monomer (I) 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 polymer of the monomer (I). The content of dimers and trimers in the crude composition may be determined by performing gel permeation chromatography (GPC) analysis of the crude composition, and calculating the ratio (area percentage) of the total peak area of ​​dimers and trimers relative to the total area of ​​each peak of the chromatogram obtained by GPC analysis.

[0411] Next, the dimer and trimer of the monomer (I) contained in the crude composition obtained by polymerization of the monomer (I) are removed from the crude composition. The means for removing the dimer and trimer is not particularly limited, and is preferably at least one means selected from the group consisting of ultrafiltration, microfiltration, dialysis membrane treatment, liquid separation and reprecipitation, more preferably at least one means selected from the group consisting of ultrafiltration, microfiltration and dialysis membrane treatment, and further preferably ultrafiltration.

[0412] It was previously unknown that dimers and trimers of monomer (I) are generated by polymerization of monomer (I), and as a result, dimers and trimers of monomer (I) are included in polymer (I). The mechanism for generating dimers and trimers of monomer (I) may not be clear, but it is speculated that dimers and trimers of monomer (I) occur at a frequency that cannot be ignored, especially among the monomers present in the polymerization system, through the polymerization reaction in the polymerization system in which monomer (I) accounts for the majority. The present invention clarifies for the first time the existence of dimers and trimers of monomer (I) in polymer (I), and for the first time finds that dimers and trimers of monomer (I) in polymer (I) can be efficiently removed from polymer (I) (crude composition) by at least one means selected from the group consisting of ultrafiltration, microfiltration and dialysis membrane treatment.

[0413] When removing dimers and trimers, usually, unreacted monomer (I) is also removed from the crude composition at the same time. Even when unreacted monomer (I) is introduced into the fluoropolymer by polymerization, it does not necessarily have an adverse effect on the function of the fluoropolymer, so the unreacted monomer (I) does not necessarily have to be removed. However, by removing the unreacted monomer (I) and the dimer and trimer at the same time in advance, the amount of monomer for polymerization can be calculated without considering the presence of the unreacted monomer (I), which has the advantage of being able to easily manufacture a fluoropolymer with a desired monomer composition. It should be noted that, even when monomer (I) remains in polymer (I) or when monomer (I) is newly added as a comonomer, among the monomers present in the polymerization system, the polymerization reaction in the polymerization system in which the fluoromonomer (wherein the monomer (I) is excluded) accounts for most of the polymerization system is also substantially not allowed to dimerize and trimerize the monomer (I), and the dimer and trimer of the monomer (I) hardly remain in the obtained fluoropolymer.

[0414] The crude composition obtained by polymerization of the monomer (I) may be a polymerized composition obtained in the polymerization, or may be a product obtained by diluting or concentrating the polymerized composition obtained in the polymerization, or may be a product subjected to a dispersion stabilization treatment, etc. In order to smoothly perform ultrafiltration, microfiltration or dialysis membrane treatment, it is also preferred to adjust the viscosity of the crude composition by these treatments.

[0415] The content of the polymer of the monomer (I) in the crude composition is not particularly limited, and can be, for example, 0.1% to 20% by mass. From the perspective of the removal efficiency of dimers and trimers, the content of the polymer of the monomer (I) in the crude composition is preferably 18.0% by mass or less, more preferably 15.0% by mass or less, further preferably 12.0% 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, further preferably 1.2% by mass or more, particularly preferably 1.5% by mass or more, and most preferably 2.0% by mass or more. The content of the polymer of the monomer (I) in the crude composition can be adjusted, for example, by a method of adding water to the crude composition obtained by polymerization of the monomer (I), a method of concentrating the crude composition obtained by polymerization of the monomer (I), and the like.

[0416] The pH of the crude composition is preferably 0 to 11, more preferably 0.5 to 8.0, and even more preferably 1.0 to 7.0. The pH of the crude composition can be adjusted by adding a pH adjuster to the crude composition obtained by polymerization of the monomer (I). The pH adjuster may be an acid or a base, and examples thereof include phosphates, sodium hydroxide, potassium hydroxide, and aqueous ammonia.

[0417] Since ultrafiltration, microfiltration or dialysis membrane treatment is smoothly performed, the viscosity of the crude composition is preferably 25 mPa·s or less. The viscosity of the crude composition can be adjusted, for example, by a method of adjusting the number average molecular weight of the polymer of the monomer (I), a method of adjusting the concentration of the polymer of the monomer (I) in the crude composition, a method of adjusting the temperature of the crude composition, etc.

[0418] The ultrafiltration or microfiltration may be carried out in a cross-flow manner or a dead-end manner without limitation, but the cross-flow manner is preferred from the viewpoint of reducing membrane clogging.

[0419] The ultrafiltration can be performed using an ultrafiltration membrane. For example, the ultrafiltration can be performed using an ultrafiltration device having an ultrafiltration membrane, and centrifugal ultrafiltration, intermittent ultrafiltration, circulating ultrafiltration, etc. can be used.

[0420] The molecular weight cut-off of the above ultrafiltration membrane is usually 0.1×10 4 Da~30×10 4 The above-mentioned ultrafiltration membrane can inhibit membrane clogging and effectively reduce dimers and trimers, so the molecular weight cutoff is preferably 1.5×10 4 The molecular weight cut-off is more preferably 2.0×10 4 Da or more, particularly preferably 3.0×10 4 Da or more, most preferably 5.0×10 4 The above molecular weight cut-off can also be 8.0×10 4 In addition, from the perspective of the removal efficiency of dimers and trimers, the above molecular weight cutoff is preferably 20×10 4 Da or less, more preferably 10×10 4 Da below.

[0421] The molecular weight cutoff of the ultrafiltration membrane can be determined by, for example, allowing polystyrene of known weight average molecular weight to pass through the membrane and setting the molecular weight at which 90% of the molecular weight is blocked as the molecular weight cutoff. The quantitative determination of polystyrene can be performed using gel permeation chromatography.

[0422] The shape of the ultrafiltration membrane may be any known shape, but is not limited thereto, and includes, for example, a hollow fiber type, a flat membrane type, a spiral type, a tubular type, etc. From the viewpoint of suppressing clogging, a hollow fiber type is preferred.

[0423] The inner diameter of the hollow fiber ultrafiltration membrane is not limited, and may be, for example, 0.1 mm to 2 mm, preferably 0.8 mm to 1.4 mm.

[0424] The length of the hollow fiber ultrafiltration membrane is not limited, and may be, for example, 0.05 m to 3 m, preferably 0.05 m to 2 m.

[0425] The material of the ultrafiltration membrane is not particularly limited, and examples thereof 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, polytetrafluoroethylene, metals such as stainless steel, and inorganic materials such as ceramics.

[0426] The material of the ultrafiltration membrane is preferably an organic material, more preferably chlorinated polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, polysulfone or polyethersulfone, further preferably polyacrylonitrile, polysulfone or polyvinylidene fluoride.

[0427] Specific examples of the ultrafiltration membrane include G-5, G-10, G-20, G-50, PW, and HWS UF manufactured by DESAL; 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 manufactured by KOCH; SPE1, SPE3, SPE5, SPE10, SPE30, SPV5, SPV50, and SOW30 manufactured by Synder; Microza (registered trademark) UF series manufactured by Asahi Kasei Corporation; NTR7410 manufactured by Nitto Denko Corporation, and the like.

[0428] From the perspective of dimer and trimer removal efficiency, the ultrafiltration is preferably performed at a pressure of 0.01 MPa or more, more preferably 0.03 MPa or more, and even more preferably 0.05 MPa or more. In addition, from the perspective of pressure resistance, the pressure is preferably 0.5 MPa or less, more preferably 0.25 MPa or less, and even more preferably 0.2 MPa or less.

[0429] From the perspective of the removal efficiency of dimers and trimers, the above-mentioned 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, and is preferably carried out at a flow rate of 5000 mL / min or less, more preferably at a flow rate of 1000 mL / min or less.

[0430] The microfiltration can be performed using a microfiltration membrane. The microfiltration membrane generally has an average pore size of 0.05 μm to 1.0 μm.

[0431] Since dimers and trimers can be effectively removed, the average pore size of the microfiltration membrane is preferably 0.1 μm or more. It is more preferably 0.075 μm or more, and further preferably 0.1 μm or more. In addition, the average pore size is preferably 1.00 μm or less. The average pore size is more preferably 0.50 μm or less, and further preferably 0.25 μm or less.

[0432] The average pore size of the microfiltration membrane can be measured according to ASTM F316 03 (bubble point method).

[0433] The shape of the microfiltration membrane may be any known shape, but is not limited thereto, and includes, for example, a hollow fiber type, a flat membrane type, a spiral type, a tubular type, etc. From the viewpoint of suppressing clogging, a hollow fiber type is preferred.

[0434] The inner diameter of the hollow fiber ultrafiltration membrane is not limited, and may be, for example, 0.1 mm to 2 mm, preferably 0.8 mm to 1.4 mm.

[0435] The length of the hollow fiber ultrafiltration membrane is not limited, and may be, for example, 0.05 m to 3 m, preferably 0.05 m to 2 m.

[0436] As the material of the microfiltration membrane, for example, cellulose, aromatic polyamide, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, polytetrafluoroethylene, ceramics, metals, etc. Among them, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate or polytetrafluoroethylene is preferred, and polyacrylonitrile or polyvinylidene fluoride is particularly preferred.

[0437] Specific examples of microfiltration membranes include Cefilt manufactured by Nippon Insulator Co., Ltd.; Microza U series and Microza P series manufactured by Asahi Kasei Corporation; Poreflon SPMW, Poreflon OPMW, and Poreflon PM manufactured by Sumitomo Electric Industries, Ltd.; Trefil manufactured by Toray Industries, Ltd.; NADIR MP005 and NADIR MV020 manufactured by MICRODYN-NADIR; and X-flow manufactured by Norit Co., Ltd.

[0438] From the perspective of dimer and trimer removal efficiency, the microfiltration is preferably performed at a pressure of 0.01 MPa or more, more preferably 0.03 MPa or more, and even more preferably 0.05 MPa or more. In addition, from the perspective of pressure resistance, the pressure is preferably 0.5 MPa or less, more preferably 0.25 MPa or less, and even more preferably 0.2 MPa or less.

[0439] From the perspective of the removal efficiency of dimers and trimers, the above-mentioned 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, and is preferably carried out at a flow rate of 5000 mL / min or less, more preferably at a flow rate of 1000 mL / min or less.

[0440] The above-mentioned dialysis membrane treatment is performed using a dialysis membrane. The dialysis membrane usually has a dialysis capacity of 0.05×10 4 Da~100×10 4 Da molecular weight cut-off.

[0441] The molecular weight cutoff of the dialysis membrane is preferably 0.3×10 4 The molecular weight cut-off is more preferably 0.5×10 4 Da or more, more preferably 1.0×10 4 Da or more, more preferably 1.5×10 4 Da or more, particularly preferably 2.0×10 4 Da or more, particularly preferably 3.0×10 4 Da or more, most preferably 5.0×10 4 The above molecular weight cut-off can also be 8.0×10 4 Big or above.

[0442] In addition, from the perspective of the removal efficiency of dimers and trimers, the molecular weight cutoff is preferably 20×10 4 Da or less, more preferably 10×10 4 Da below.

[0443] The molecular weight cut-off of the dialysis membrane can be measured, for example, using the same method as that for the ultrafiltration membrane.

[0444] The material of the dialysis membrane is not particularly limited, and examples thereof include cellulose, polyacrylonitrile, polymethyl methacrylate, ethylene vinyl alcohol copolymer, polysulfone, polyamide, and polyester-based polymer alloys.

[0445] Specific examples of the dialysis membrane include Spectra / Por (registered trademark) Float-A-Lyzer, Tube-A-Lyzer, Dialysis tubing, 6Dialysis tubing, and 7Dialysis tubing manufactured by Spectrum Laboratories.

[0446] The ultrafiltration, microfiltration or dialysis membrane treatment is preferably performed at a temperature of 10°C or higher. It is more preferably 15°C or higher, further 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 more efficiently reduced. The temperature is preferably 90°C or lower, more preferably 80°C or lower, further preferably 70°C or lower, and particularly preferably 60°C or lower.

[0447] Ultrafiltration, microfiltration or dialysis membrane treatment can be performed while adding water to the crude composition or adjusting the pH of the crude composition. Water can be added to the crude composition intermittently or continuously.

[0448] The endpoint of ultrafiltration, microfiltration or dialysis membrane treatment can be appropriately determined without limitation. In addition, in the above-mentioned ultrafiltration, microfiltration or dialysis membrane treatment, in order to improve the durability of the filter membrane, the filtration time of 1 hour to 24 hours can be used as a benchmark, and backwashing is carried out once or so with water.

[0449] Liquid separation can be carried out, for example, by adding an organic solvent to the composition to separate it into two phases, an aqueous phase and an organic solvent phase, and recovering the aqueous phase.

[0450] Reprecipitation can be carried out, for example, by dropping the composition into a poor solvent to precipitate the polymer, recovering the precipitated polymer, dissolving the recovered polymer in a good solvent, dropping the resulting solution into a poor solvent to precipitate the polymer again, and recovering the precipitated polymer.

[0451] By removing dimer and trimer of monomer (I) from the crude composition of the polymer containing monomer (I), usually, obtain an aqueous solution containing the polymer (I) that does not substantially contain dimer and trimer. The polymer (I) used in the manufacture method of the present invention can be the polymer (I) contained in the obtained aqueous solution, or can be the polymer (I) obtained by separating from the aqueous solution. The method for separating polymer (I) from the aqueous solution is not particularly limited. For example, the polymer (I) can be separated by methods such as precipitation, cleaning, drying of the polymer (I) in the aqueous solution.

[0452] As the polymer (I), an aqueous solution containing the polymer (I) can be used. The preferred content of the dimer and trimer of the monomer (I) relative to the polymer (I) in the aqueous solution is as described above as the content of the dimer and trimer in the polymer (I).

[0453] <Polymerization of fluorinated monomers>

[0454] In the production method of the present invention, a fluorinated monomer is polymerized in an aqueous medium. As the fluorinated monomer, it is preferred to have at least one double bond. As the above-mentioned fluorinated monomer, it is preferred to be selected from tetrafluoroethylene [TFE], hexafluoropropylene [HFP], trifluorochloroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkyl ethylene, fluoroalkyl allyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, general formula (100): CHX 101 =CX 102 R 101 (Where X101 and X 102 One of them is H and the other is F, Rf 101 It is at least one member selected from the group consisting of a fluorinated monomer represented by a linear or branched fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated vinyl heterocyclic body, and a monomer providing a crosslinking site.

[0455] As the fluoroalkyl vinyl ether, for example, at least one selected from the group consisting of the following fluorinated monomers is preferred, and the monomer is:

[0456] General formula (110): CF 2 =CF-ORf 111

[0457] (Where Rf 111 represents a perfluorinated organic group),

[0458] General formula (120): CF 2 =CF-OCH 2 -Rf 121

[0459] (Where Rf 121 is a fluorine-containing monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms,

[0460] General formula (130): CF 2 =CFOCF 2 O 131

[0461] (Where Rf 131 a fluorine-containing monomer represented by a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms,

[0462] General formula (140): CF 2 =CFO(CF 2 CF(Y 141 )O) m (CF 2 ) n F

[0463] (Where Y 141 represents a fluorine atom or a trifluoromethyl group. m is an integer of 1 to 4. n is an integer of 1 to 4) and

[0464] General formula (150): CF 2 =CF-O-(CF 2 CFY 151 -O)n-(CFY 152) m -A 151

[0465] (Where Y 151 Indicates fluorine atom, chlorine atom, -SO 2 F or perfluoroalkyl. The perfluoroalkyl group may contain ethereal oxygen and -SO 2 F group. n represents an integer of 0 to 3. n Y 151 Can be the same or different. 152 Represents a fluorine atom, a chlorine atom, or -SO 2 F group. m represents an integer of 1 to 5. m Y 152 Can be the same or different. 151 Indicates -SO 2 X 151 、-COZ 151 or-POZ 152 Z 153 .X 151 Indicates F, Cl, Br, I, -OR 151 or -NR 152 R 153 . Z 151 , Z 152 and Z 153 Same or different, indicates -NR 154 R 155 OR 156 . R 151 , R 152 , R 153 , R 154 , R 155 and R 156 The fluorine-containing monomer is the same or different and represents H, ammonium, an alkali metal, an alkyl group containing or not containing a fluorine atom, an aryl group, or a sulfonyl group-containing group).

[0466] In the present invention, the "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0467] Examples of the fluorinated monomer represented by the general formula (110) include Rf 111 It is a fluorine-containing monomer having a perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

[0468] Examples of the perfluoro organic group in the general formula (110) include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0469] As the fluorinated monomer represented by the general formula (110), further examples include Rf in the general formula (110):111 It is a monomer of a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 111 is the following formula:

[0470] [Chemistry 14]

[0471]

[0472] (wherein m represents 0 or an integer of 1 to 4) represented by a monomer, Rf 111 is the following formula:

[0473] [Chemistry 15]

[0474]

[0475] (wherein n represents an integer of 1 to 4) and the like.

[0476] As the fluorine-containing monomer represented by the general formula (110), preferably

[0477] General formula (160): CF 2 =CF-ORf 161

[0478] (Where Rf 161 represents a fluorinated monomer represented by a perfluoroalkyl group having 1 to 10 carbon atoms. 161 A perfluoroalkyl group having 1 to 5 carbon atoms is preferred.

[0479] The fluoroalkyl vinyl ether is preferably at least one selected from the group consisting of fluorinated monomers represented by general formulae (160), (130) and (140).

[0480] As the fluorine-containing monomer represented by the general formula (160), it is preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether) and perfluoro(propyl vinyl ether), and more preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether) and perfluoro(propyl vinyl ether).

[0481] The fluorine-containing monomer represented by the general formula (130) is preferably selected from the group consisting of CF 2 =CFOCF 2 OCF 3 CF 2 =CFOCF 2 OCF 2 CF 3 and CF 2 =CFOCF 2 OCF 2 CF 2 OCF 3 At least one of the group consisting of.

[0482] The fluorinated monomer represented by the general formula (140) is preferably selected from the group consisting of CF 2 =CFOCF 2 CF(CF 3 )O(CF 2 ) 3 F. CF 2 =CFO(CF 2 CF(CF 3 )O) 2 (CF 2 ) 3 F and CF 2 =CFO(CF 2 CF(CF 3 )O) 2 (CF 2 ) 2 At least one of the group consisting of F.

[0483] The fluorine-containing monomer represented by the general formula (150) is preferably selected from the group consisting of CF 2 =CFOCF 2 CF 2 SO 2 F. CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F. CF 2 =CFOCF 2 CF(CF 2 CF 2 SO 2 F)OCF 2 CF 2 SO 2 F and CF 2 =CFOCF 2 CF(SO 2 F) 2 At least one of the group consisting of.

[0484] As the fluorinated monomer represented by the general formula (100), Rf is preferably 101 is a fluorinated monomer having a linear fluoroalkyl group, more preferably Rf 101 It is a straight-chain perfluoroalkyl fluorinated monomer. 101 The number of carbon atoms in is preferably 1 to 6. Examples of the fluorine-containing monomer represented by the general formula (100) include CH 2 =CFCF 3 , CH 2 =CFCF 2 CF3 , CH 2 =CFCF 2 CF 2 CF 3 , CH 2 =CFCF 2 CF 2 CF 2 H, CH 2 =CFCF 2 CF 2 CF 2 CF 3 、CHF=CHCF 3 (E body), CHF=CHCF 3 (Z-body), etc., among which CH 2 =CFCF 3 2,3,3,3-tetrafluoropropene shown.

[0485] As the fluoroalkylethylene, preferably

[0486] General formula (170): CH 2 =CH-(CF 2 ) n -X 171

[0487] (Where X 171 is H or F, n is an integer of 3 to 10), more preferably a fluoroalkylethylene selected from CH 2 =CH-C 4 F 9 and CH 2 =CH-C 6 F 13 At least one of the group consisting of.

[0488] Examples of the fluoroalkyl allyl ether include

[0489] General formula (180): CF 2 =CF-CF 2 -ORf 111

[0490] (Where Rf 111 represents a perfluorinated organic group).

[0491] Rf of general formula (180) 111 With the Rf of general formula (110) 111 Same as Rf 111 , preferably a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms. The fluoroalkyl allyl ether represented by the general formula (180) is preferably selected from CF2 =CF-CF 2 -O-CF 3 CF 2 =CF-CF 2 -OC 2 F 5 CF 2 =CF-CF 2 -OC 3 F 7 and CF 2 =CF-CF 2 -OC 4 F 9 At least one of the group consisting of, more preferably selected from CF 2 =CF-CF 2 -OC 2 F 5 CF 2 =CF-CF 2 -OC 3 F 7 and CF 2 =CF-CF 2 -OC 4 F 9 At least one of the group consisting of, more preferably CF 2 =CF-CF 2 -O-CF 2 CF 2 CF 3 .

[0492] Examples of the fluorinated vinyl heterocyclic compound include those of the general formula (230):

[0493] [Chemistry 16]

[0494]

[0495] (Where X 231 and X 232 are independently F, Cl, methoxy or fluoromethoxy, Y 231 Formula Y 232 Or Y 233 .

[0496] [Chemistry 17]

[0497]

[0498] (Where Z 231 and Z 232 and (ii) independently represents F or a fluoroalkyl group having 1 to 3 carbon atoms.

[0499] As the monomer providing a crosslinking site, at least one monomer selected from the group consisting of the following monomers is preferred:

[0500] General formula (180): CX 181 2 =CX 182 -R f 181 CHR 181 X 183

[0501] (Where X 181 and X 182 are independently a hydrogen atom, a fluorine atom or CH 3 , R f 181 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R 181 A hydrogen atom or CH 3 , X 183 is an iodine atom or a bromine atom),

[0502] General formula (190): CX 191 2 =CX 192 -R f 191 X 193

[0503] (Where X 191 and X 192 are independently a hydrogen atom, a fluorine atom or CH 3 , R f 191 is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, X 193 is an iodine atom or a bromine atom),

[0504] General formula (200): CF 2 =CFO(CF 2 CF(CF 3 )O) m (CF 2 ) n -X 201

[0505] (wherein, m is an integer from 0 to 5, n is an integer from 1 to 3, and X 201 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom or a -CH 2 I) the fluorine-containing monomer, and

[0506] General formula (210): CH 2 =CFCF2 O(CF(CF 3 )CF 2 O) m (CF(CF 3 )) n -X 211

[0507] (wherein, m is an integer from 0 to 5, n is an integer from 1 to 3, and X 211 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom or a -CH 2 OH) represented by a fluorinated monomer, and

[0508] General formula (220): CR 221 R 222 =CR 223 -Z 221 -CR 224 =CR 225 R 226

[0509] (Where R 221 , R 222 , R 223 , R 224 , R 225 and R 226 are the same or different and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 221 A linear or branched alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, an at least partially fluorinated alkylene group having 1 to 10 carbon atoms, or an oxyalkylene group;

[0510] -(Q) p -CF 2 O-(CF 2 CF 2 O) m (CF 2 O) n -CF 2 -(Q) p -

[0511] (wherein, Q is an alkylene group or an oxyalkylene group. p is 0 or 1. m / n is 0.2 to 5) and a monomer represented by a (per)fluoropolyoxyalkylene group having a molecular weight of 500 to 10000).

[0512] X 183 and X 193 Preferably it is an iodine atom. f 181 and R f 191 It is preferably a perfluoroalkylene group having 1 to 5 carbon atoms.181 Preferably, it is a hydrogen atom. 201 Preferably, it is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom or a -CH 2 I. X 211 Preferably, it is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom or a -CH 2 OH.

[0513] As the monomer providing a crosslinking site, it is preferably selected from the group consisting of CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN、CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 COOH、CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CH 2 I. CF 2 =CFOCF 2 CF 2 CH 2 I. CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )CN、CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )COOH、CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )CH 2 OH, CH 2 =CHCF 2 CF 2 I. CH 2 =CH(CF 2 ) 2 CH=CH 2 , CH 2 =CH(CF 2 ) 6 CH=CH 2 and CF 2=CFO(CF 2 ) 5 At least one of the group consisting of CN, more preferably selected from CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN and CF 2 =CFOCF 2 CF 2 CH 2 At least one of the group consisting of I.

[0514] In the above-mentioned polymerization, the above-mentioned fluorine-containing monomer and the non-fluorine-containing monomer can be polymerized. Examples of the above-mentioned non-fluorine-containing monomer include hydrocarbon monomers reactive with the above-mentioned fluorine-containing monomer. Examples of the above-mentioned hydrocarbon monomer include olefins such as ethylene, propylene, butene, and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl octanoate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristic acid, vinyl palmitic acid, vinyl stearate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl cyclohexanecarboxylate, and monochloroacetic acid. Vinyl esters such as vinyl ester, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, vinyl undecylenate, vinyl hydroxyacetate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, vinyl hydroxycyclohexanecarboxylate; alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, cyclohexyl allyl ether; alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester; and the like.

[0515] In addition, the above-mentioned non-fluorine-containing monomer may also be a hydrocarbon monomer containing a functional group (except for monomers providing a crosslinking site). Examples of the above-mentioned hydrocarbon monomer containing a functional group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; non-fluorine-containing monomers having a carboxyl group such as itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride, and perfluorobutenoic acid; non-fluorine-containing monomers having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether; non-fluorine-containing monomers having an amino group such as aminoalkyl vinyl ether and aminoalkyl allyl ether; non-fluorine-containing monomers having an amide group such as (meth)acrylamide and hydroxymethyl acrylamide; and the like.

[0516] In the above-mentioned polymerization, by polymerizing one or more of the above-mentioned fluorinated monomers, particles of a desired fluorinated polymer can be obtained.

[0517] The amount of polymer (I) added in the above polymerization is preferably 0.0001% to 10% by mass relative to the aqueous medium, with a more preferred lower limit of 0.001% by mass and a more preferred upper limit of 1% by mass. By making the amount of polymer (I) added within the above range, the polymerization of the fluorinated monomer in the aqueous medium can be smoothly carried out. The amount of polymer (I) added is the total amount of polymer (I) added in the above polymerization.

[0518] In the above-mentioned polymerization, polymer (I) can be added once or continuously. Adding polymer (I) continuously means, for example, adding polymer (I) not once but over time and continuously or in batches. In the above-mentioned polymerization, an aqueous solution comprising polymer (I) and water can also be prepared and added.

[0519] In the above-mentioned polymerization, it is preferred to start the addition of polymer (I) before the solid content of the fluoropolymer formed in the aqueous medium reaches 0.5 mass %, and then continuously add polymer (I). As the period for starting to add polymer (I), it is preferred that the solid content of the fluoropolymer reaches 0.3 mass %, more preferably before reaching 0.2 mass %, further preferably before reaching 0.1 mass %, and particularly preferably at the same time as the start of polymerization. The above-mentioned solid content is the total content of the fluoropolymer relative to the aqueous medium and the fluoropolymer.

[0520] In the above-mentioned polymerization, at least one polymer (I) can be used to effectively manufacture the fluorinated polymer. In addition, compounds contained in two or more polymers (I) can be used simultaneously, as long as they are volatile substances or substances that can remain in a molded body composed of the fluorinated polymer, and other compounds with surface activity other than the polymer (I) can also be used simultaneously.

[0521] In the above-mentioned polymerization, a nucleating agent can be used. The amount of the nucleating agent added can be appropriately selected according to the type of the nucleating agent. As the amount of the nucleating agent added, relative to the aqueous medium, it can be 5000 mass ppm or less, preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, further preferably 100 ppm or less, particularly preferably 50 mass ppm or less, and most preferably 10 mass ppm or less.

[0522] In the above polymerization, the nucleating agent is preferably added to the aqueous medium before the polymerization starts or before the solid content of the fluorinated polymer formed in the aqueous medium reaches 5.0 mass %. By adding the nucleating agent at the initial stage of the polymerization, an aqueous dispersion having a small average primary particle size and excellent stability can be obtained.

[0523] The amount of the nucleating agent added in the initial stage of polymerization is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more relative to the obtained fluorinated polymer. The upper limit of the amount of the nucleating agent added in the initial stage of polymerization is not limited, and is, for example, 2000% by mass.

[0524] By using a nucleating agent, a fluorine-containing polymer having a smaller primary particle size can be obtained compared with polymerization carried out in the absence of the nucleating agent.

[0525] Examples of the nucleating agent include dicarboxylic acids, perfluoropolyether (PFPE) acids or salts thereof, hydrocarbon-containing surfactants, etc. The nucleating agent preferably does not contain an aromatic ring, and is preferably an aliphatic compound.

[0526] The nucleating agent is preferably added before or simultaneously with the addition of the polymerization initiator. The particle size distribution can also be adjusted by adding the nucleating agent during the polymerization.

[0527] The amount of the dicarboxylic acid is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 100 ppm by mass or less, relative to the aqueous medium.

[0528] The above-mentioned perfluoropolyether (PFPE) acid or its salt may have any chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. In addition, two or more fluorocarbon groups may exist in the molecule. A representative structure has a repeating unit represented by the following formula.

[0529] (-CFCF 3 -CF 2 -O-) n (VII)

[0530] (-CF 2 -CF 2 -CF 2 -O-) n (VIII)

[0531] (-CF 2 -CF 2 -O-) n -(-CF 2 -O-) m (IX)

[0532] (-CF 2 -CFCF 3 -O-) n -(-CF 2 -O-) m (X)

[0533] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed in the document, the PFPE acid or its salt may have a carboxylic acid group or its salt at one or both ends. In addition, the PFPE acid or its salt may have a sulfonic acid, phosphonic acid group or its salt at one or both ends. In addition, the PFPE acid or its salt may have different groups at each end. For monofunctional PFPE, the other end of the molecule is usually perfluorinated and may also contain hydrogen or chlorine atoms. The PFPE acid or its salt has at least 2 ether oxygens, preferably at least 4 ether oxygens, and more preferably at least 6 ether oxygens. Preferably, at least one of the fluorocarbon groups separated by the ether oxygen, more preferably at least two of such fluorocarbon groups have 2 or 3 carbon atoms. More preferably, at least 50% of the fluorocarbon groups separated by the ether oxygen have 2 or 3 carbon atoms. In addition, preferably, the PFPE acid or its salt has a total of at least 15 carbon atoms, for example, the preferred minimum value of n or n+m in the repeating unit structure is at least 5. Two or more PFPE acids or salts thereof having an acid group at one or both ends can be used in the production method of the present invention. The PFPE acid or salt thereof preferably has a number average molecular weight of less than 6000 g / mol.

[0534] The amount of the hydrocarbon-containing surfactant added is preferably less than 40 mass ppm, more preferably less than 30 mass ppm, and further preferably less than 20 mass ppm relative to the aqueous medium. It is inferred that the ppm amount of the lipophilic nucleating site present in the aqueous medium is less than the above-mentioned amount added. Therefore, the amount of the lipophilic nucleating site is less than the above-mentioned 40 mass ppm, 30 mass ppm, and 20 mass ppm, respectively. It is believed that the lipophilic nucleating site exists as a molecule, so even a very small amount of the hydrocarbon-containing surfactant can generate a large amount of lipophilic nucleating sites. Therefore, even if only about 1 mass ppm of the hydrocarbon-containing surfactant is added to the aqueous medium, a beneficial effect can be obtained. The preferred lower limit is 0.01 mass ppm, and the more preferred lower limit is 0.1 mass ppm.

[0535] The hydrocarbon-containing surfactants include silicone surfactants such as those disclosed in US Pat. No. 7,897,682 (Brothers et al.) and US Pat. No. 7,977,438 (Brothers et al.), and include nonionic surfactants and cationic surfactants.

[0536] As the hydrocarbon-containing surfactant, a nonionic surfactant (for example, a nonionic hydrocarbon surfactant) is preferred. That is, as the nucleating agent, a nonionic surfactant is preferred. The nonionic surfactant preferably does not contain an aromatic moiety.

[0537] Examples of the nonionic surfactant include the following general formula (i):

[0538] R 3 -OA 1 -H(i)

[0539] (Where R 3 is a straight-chain or branched primary or secondary alkyl group having 8 to 18 carbon atoms, 1 is a compound represented by a polyoxyalkylene chain).

[0540] R 3 The number of carbon atoms in R is preferably 10 to 16, more preferably 12 to 16. 3 If the number of carbon atoms in R is 18 or less, it is easy to obtain good dispersion stability of the aqueous dispersion. 3 If the number of carbon atoms exceeds 18, the flow temperature is high and it is difficult to handle. 3 When the number of carbon atoms is less than 8, the surface tension of the aqueous dispersion increases, and the permeability and wettability tend to decrease.

[0541] The polyoxyalkylene chain may be composed of ethylene oxide and propylene oxide. The polyoxyalkylene chain is composed of an average repeating number of ethylene oxide groups of 5 to 20 and an average repeating number of propylene oxide groups of 0 to 2, and is a hydrophilic group. The number of ethylene oxide units may include any of the broad or narrow unimodal distributions generally provided, or a broader or bimodal distribution obtained by blending. When the average repeating number of propylene oxide groups exceeds 0, the ethylene oxide groups and propylene oxide groups in the polyoxyalkylene chain may be arranged in blocks or randomly.

[0542] From the viewpoint of the viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain consisting of an average repeating number of oxyethylene groups of 7 to 12 and an average repeating number of oxypropylene groups of 0 to 2 is preferred. 1 It is preferred that the polyurethane foam has an average of 0.5 to 1.5 oxypropylene groups because low foaming properties are good.

[0543] More preferably R 3 (R')(R")HC-, wherein R' and R" are the same or different linear, branched or cyclic alkyl groups, and the total number of carbon atoms is at least 5, preferably 7 to 17. Preferably, at least one of R' or R" is a branched or cyclic hydrocarbon group.

[0544] Specific examples of the polyoxyethylene alkyl ether include C 13 H 27 -O-(C 2 H 4 O) 10 -H, C 12 H 25 -O-(C 2 H 4 O) 10 -H, C 10 H 21 CH(CH 3 )CH 2 -O-(C 2 H 4 O) 9 -H, C 13 H 27 -O-(C 2 H 4 O) 9 -(CH(CH 3 )CH 2 O)-H, C 16 H 33 -O-(C 2 H 4 O) 10 -H、HC(C 5 H 11 )(C 7 H 15 )-O-(C 2 H 4 O) 9 -H, etc. Commercially available products of the above-mentioned polyoxyethylene alkyl ethers include, for example, Genapol X080 (product name, manufactured by Clariant), Noigen TDS series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) exemplified by Noigen TDS-80 (trade name), Leocol TD series (manufactured by LION) exemplified by Leocol TD-90 (trade name), LIONOL (registered trademark) TD series (manufactured by LION), T-Det A series (manufactured by Harcros Chemicals) exemplified by T-Det A138 (trade name), TERGITOL (registered trademark) 15S series (manufactured by The Dow Chemical Company), and the like.

[0545] The nonionic surfactant is also preferably an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 4 to about 18 ethylene oxide units, an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 6 to about 12 ethylene oxide units, or a mixture thereof. This type of nonionic surfactant is also commercially available as TERGITOLTMN-6, TERGITOLTMN-10, and TERGITOLTMN-100X (all product names, manufactured by The Dow Chemical Company).

[0546] In addition, the hydrophobic group of the nonionic surfactant may be any of an alkylphenol group, a linear alkyl group, and a branched alkyl group.

[0547] For example, examples of polyoxyethylene alkylphenyl ether-based nonionic compounds include the following general formula (ii):

[0548] R 4 -C 6 H 4 -OA 2 -H(ii)

[0549] (Where R 4 is a straight-chain or branched primary or secondary alkyl group having 4 to 12 carbon atoms, 2 Specific examples of the polyoxyethylene alkylphenyl ether-based nonionic compound include TRITON X-100 (trade name, manufactured by The Dow Chemical Company).

[0550] Examples of the nonionic surfactant include polyol compounds, and specific examples include polyol compounds described in International Publication No. 2011 / 014715.

[0551] As typical examples of polyol compounds, compounds having one or more sugar units as polyol units can be cited. The sugar unit can be modified to contain at least one long chain. As suitable polyol compounds containing at least one long chain portion, for example, alkyl glycosides, modified alkyl glycosides, sugar esters and combinations thereof can be cited. As sugars, monosaccharides, oligosaccharides and sorbitan can be cited, but are not limited to them. As monosaccharides, pentose and hexose can be cited. As typical examples of monosaccharides, ribose, glucose, galactose, mannose, fructose, arabinose, and xylose can be cited. As oligosaccharides, oligomers of 2 to 10 identical or different monosaccharides can be cited. As examples of oligosaccharides, sucrose, maltose, lactose, raffinose and isomaltose can be cited, but are not limited to them.

[0552] Typically, sugars suitable for use as polyol compounds include cyclic compounds containing a five-membered ring of 4 carbon atoms and 1 heteroatom (typically oxygen or sulfur, preferably an oxygen atom), or cyclic compounds containing a six-membered ring of 5 carbon atoms and the above-mentioned 1 heteroatom, preferably an oxygen atom. They further contain at least 2 or at least 3 hydroxyl groups (-OH groups) bonded to carbon ring atoms. Typically, in order to form an ether or ester bond between the long-chain residue and the sugar part, the sugar is modified in the following aspects: one or more of the hydrogen atoms of the hydroxyl group (and / or hydroxyalkyl group) bonded to the carbon ring atom are replaced by a long-chain residue.

[0553] The sugar polyol may contain one sugar unit or two or more sugar units. One sugar unit or two or more sugar units may be modified by the above-mentioned long chain part. Specific examples of sugar polyol compounds include glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof.

[0554] Preferred types of polyol compounds are alkyl or modified alkyl glucosides. These types of surfactants contain at least one glucose moiety. Examples include

[0555] [Chemistry 18]

[0556]

[0557] (wherein x represents 0, 1, 2, 3, 4, or 5, R 1 and R 2 independently represents H or a long chain unit containing at least 6 carbon atoms, wherein R 1 and R 2 In the compound represented by (i) wherein at least one of the R 1 and R 2 Typical examples of the aliphatic alcohol residue include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof.

[0558] The above formula shows a specific example of an alkyl polyglucoside representing the pyranose form of glucose, but it will be appreciated that other sugars or sugars of the same sugar but in different mirror isomer or diastereomeric forms may also be used.

[0559] Alkyl glucoside can be obtained, for example, by the acid-catalyzed reaction of glucose, starch, or n-butyl glucoside with aliphatic alcohols. In a typical example, a mixture of various alkyl glucosides is obtained (Alkylpolygylcoside, Rompp, LexikonChemie, Version 2.0, Stuttgart / New York, Georg Thieme Verlag, 1999). Examples of aliphatic alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof. In addition, alkyl glucoside is commercially available from Cognis GmbH, Düsseldorf, Germany, under the trade name GLUCOPON or DISPONIL.

[0560] Other nonionic surfactants include bifunctional block copolymers supplied by BASF as the Pluronic (registered trademark) R series, tridecanol alkoxylates supplied by BASF as the Iconol (registered trademark) TDA series, and hydrocarbon-containing siloxane surfactants, preferably hydrocarbon surfactants. Here, when the above-mentioned hydrocarbon groups are replaceable by halogens such as fluorine, they are completely replaced by hydrogen atoms, so that these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituent on the hydrocarbon group is hydrogen.

[0561] In the above polymerization, a compound having a functional group capable of free radical polymerization and a hydrophilic group may be used together with the polymer (I). As the compound having a functional group capable of free radical polymerization and a hydrophilic group, the same compounds as those described later as the modified monomer (A) may be used.

[0562] In the above polymerization, in addition to the polymer (1) and other compounds having surface activity as desired, additives for stabilizing the compounds may be used. Examples of the above additives include buffers, pH adjusters, stabilizing aids, and dispersion stabilizers.

[0563] As the stabilizing aid, paraffin, fluorine oil, fluorine solvent, silicone oil and the like are preferred. The stabilizing aid can be used alone or in combination of two or more. As the stabilizing aid, paraffin is more preferred. Paraffin can be liquid, semi-solid or solid at room temperature, but preferably a saturated hydrocarbon having 12 or more carbon atoms. The melting point of paraffin is usually preferably 40°C to 65°C, more preferably 50°C to 65°C.

[0564] The amount of the stabilizing agent used is preferably 0.1 to 12% by mass, more preferably 0.1 to 8% by mass, based on the mass of the aqueous medium used. The stabilizing agent is preferably sufficiently hydrophobic to be completely separated and removed from the aqueous dispersion after polymerization and not to become a contaminating component.

[0565] The above-mentioned polymerization can be carried out as follows: an aqueous medium, the above-mentioned polymer (I), a monomer and other additives as required are put into a polymerization reactor, the contents of the reactor are stirred, and the reactor is maintained at a specified polymerization temperature, and then a specified amount of a polymerization initiator is added to initiate a polymerization reaction, thereby polymerization can be carried out. After the polymerization reaction starts, monomers, polymerization initiators, chain transfer agents and polymer (I) etc. can be added according to the purpose. Polymer (I) can also be added after the polymerization reaction starts.

[0566] Usually, the polymerization temperature is 5° C. to 120° C., and the polymerization pressure is 0.05 MPaG to 10 MPaG. The polymerization temperature and the polymerization pressure are appropriately determined depending on the type of monomers used, the molecular weight of the target fluorine-containing polymer, and the reaction rate.

[0567] The polymerization initiator is not particularly limited as long as it can generate free radicals in the above polymerization temperature range, and a known oil-soluble and / or water-soluble polymerization initiator can be used. Furthermore, it can also be combined with a reducing agent to initiate polymerization in a redox form. The concentration of the polymerization initiator is appropriately determined according to the type of monomer, the molecular weight of the target fluorinated polymer, and the reaction rate.

[0568] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0569] The oil-soluble free radical polymerization initiator may be a known oil-soluble peroxide, and for example, the following peroxides may be cited as representative substances: dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate; dialkyl peroxides such as di-tert-butyl peroxide; and di(ω-hydro-dodecafluorohexanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexadecanoyl) peroxide, di(ω-hydro-hexadecanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluoropentanoyl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide. peroxide, di(perfluorononanoyl)peroxide, di(ω-chloro-hexafluorobutyryl)peroxide, di(ω-chloro-decafluorohexanoyl)peroxide, di(ω-chloro-tetrafluorooctanoyl)peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydro-dodecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutyryl)peroxide, di(trichlorooctafluorohexanoyl)peroxide, di(tetrachloroundecanoyl)peroxide, di(pentachlorotetrafluorodecanoyl)peroxide, di(undecanotridodecanoyl)peroxide and the like di[perfluoro(or fluorochloro)acyl]peroxides; and the like.

[0570] As the water-soluble free radical polymerization initiator, it can be a known water-soluble peroxide, for example, ammonium salts, potassium salts, sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonic acid, etc., organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide, tert-butyl peroxymaleate, tert-butyl hydroperoxide, etc. It can also contain a reducing agent such as sulfites and sulfites, and its amount can be 0.1 to 20 times that of the peroxide.

[0571] For example, in the case of implementing polymerization at a low temperature below 30°C, etc., as a polymerization initiator, it is preferred to use a redox initiator composed of an oxidant and a reducing agent. As the oxidant, persulfate, organic peroxide, potassium permanganate, manganese triacetate, ammonium cerium nitrate, etc. can be mentioned. As the reducing agent, sulfite, bisulfite, bromate, diimide, oxalic acid, etc. can be mentioned. As persulfate, ammonium persulfate and potassium persulfate can be mentioned. As sulfite, sodium sulfite and ammonium sulfite can be mentioned. In order to increase the decomposition rate of the initiator, it is also preferred to add copper salts and iron salts to the combination of redox initiators. As the copper salt, copper (II) sulfate can be mentioned, and as the iron salt, iron (II) sulfate can be mentioned.

[0572] As the above-mentioned redox initiator, for example, potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / ferric sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / bisulfite, etc. can be mentioned, preferably potassium permanganate / oxalic acid. In the case of using a redox initiator, either the oxidant or the reductant can be put into a polymerization kettle in advance, and then the other can be added continuously or intermittently to initiate polymerization. For example, in the case of using potassium permanganate / oxalic acid, it is preferred to put oxalic acid into the polymerization kettle and continuously add potassium permanganate thereto.

[0573] The amount of polymerization initiator added is not particularly limited, and may be added once, sequentially, or continuously at the initial stage of polymerization in an amount that does not significantly reduce the polymerization rate (e.g., a concentration of several ppm relative to water). The upper limit is a range in which the heat of polymerization reaction can be used to remove heat from the device surface and the reaction temperature can be increased, and a more preferred upper limit is a range in which the heat of polymerization reaction can be removed from the device surface.

[0574] The aqueous medium is a reaction medium for polymerization and is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and a non-fluorinated organic solvent such as alcohol, ether, or ketone and / or a fluorinated organic solvent having a boiling point of 40° C. or less.

[0575] In the above-mentioned polymerization, a known chain transfer agent, radical scavenger, or decomposition agent may be further added according to the purpose to adjust the polymerization rate and molecular weight.

[0576] Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate; and various halogenated hydrocarbons such as isopentane, methane, ethane, propane, methanol, isopropanol, acetone, various mercaptans, and carbon tetrachloride; and cyclohexane.

[0577] Bromine compounds or iodine compounds can be used as chain transfer agents. As a polymerization method using a bromine compound or an iodine compound, for example, a method of polymerizing a fluorinated monomer in an aqueous medium in the presence of a bromine compound or an iodine compound in a substantially oxygen-free state (iodine transfer polymerization method) can be cited. As a representative example of the bromine compound or iodine compound used, for example, the general formula:

[0578] R a I x Br y

[0579] (where x and y are integers from 0 to 2 and satisfy 1≤x+y≤2, R a is a saturated or unsaturated fluorocarbon or chlorofluorocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, wherein R aBy using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer to function as a crosslinking point.

[0580] Examples of the bromine compound or iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodoperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodoperfluoropropane, CF 2 Br 2 BrCF 2 CF 2 Br, CF 3 CFC 2 Br, CFClBr 2 BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF 2 Br, BrCF 2 CFB 3 , 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluoro-1-butene, 2-bromo-4-iodoperfluoro-1-butene, mono-iodine-mono-bromine substituted bodies, di-iodine-mono-bromine substituted bodies, and (2-iodoethyl) and (2-bromoethyl) substituted bodies of benzene, etc. These compounds can be used alone or in combination with each other.

[0581] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferably used in view of polymerization reactivity, crosslinking reactivity, and availability.

[0582] The amount of the chain transfer agent used is usually 1 to 50,000 ppm by mass, preferably 1 to 20,000 ppm by mass, based on the total amount of the fluorinated monomer supplied.

[0583] The chain transfer agent may be added to the reaction vessel all at once before the start of polymerization, may be added all at once after the start of polymerization, may be added in several portions during polymerization, or may be added continuously during polymerization.

[0584] As polymerization initiator, organic peroxides such as persulfate (for example ammonium persulfate), disuccinic acid peroxide, diglutaric acid peroxide can be used alone or in the form of these mixtures. In addition, it is also possible to share with reducing agents such as sodium sulfite to make a redox system for use. And then, in polymerization, free radical scavengers such as hydroquinone and catechol can also be added, or the decomposition agent of peroxides such as ammonium sulfite can be added to adjust the free radical concentration in the system.

[0585] In the above polymerization, the fluorinated monomer may be polymerized in an aqueous medium in the presence of the polymer (I) to produce an aqueous dispersion of fluorinated polymer particles, and in the aqueous dispersion of fluorinated polymer particles, the fluorinated monomer may be seed polymerized to form fluorinated polymer particles, thereby obtaining the fluorinated polymer.

[0586] The above-mentioned polymerization is preferably performed by polymerizing the fluorinated monomer in the substantial absence of a fluorinated surfactant.

[0587] Conventionally, a fluorinated surfactant has been used in the polymerization of a fluorinated polymer in an aqueous medium. However, according to the production method of the present invention, a fluorinated polymer can be obtained even without using a fluorinated surfactant.

[0588] In the present invention, "under the condition that there is substantially no fluorinated surfactant" means that the amount of the fluorinated surfactant relative to the aqueous medium is 10 mass ppm or less. The amount of the fluorinated surfactant relative to the aqueous medium is preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and even more preferably 1 mass ppb or less.

[0589] Examples of the fluorinated surfactant include anionic fluorinated surfactants, etc. The anionic fluorinated surfactant may be a surfactant containing fluorine atoms, wherein the total number of carbon atoms of the part excluding the anionic group is 20 or less.

[0590] Furthermore, the fluorine-containing surfactant may be a surfactant containing fluorine whose anionic part has a molecular weight of 800 or less.

[0591] It should be noted that the above-mentioned "anionic part" refers to the part of the above-mentioned fluorinated surfactant other than the cation. For example, in the F(CF 2 ) n1 In the case of COOM, it is "F(CF 2 ) n1 COO” part.

[0592] In addition, as the above-mentioned fluorinated surfactant, a fluorinated surfactant having a LogPOW of 3.5 or less can be cited. The above-mentioned LogPOW is the partition coefficient between 1-octanol and water, and is represented by LogP [wherein P represents the ratio of the fluorinated surfactant concentration in octanol to the fluorinated surfactant concentration in water when a fluorinated surfactant-containing octanol / water (1:1) mixed solution undergoes phase separation].

[0593] The above LogPOW is calculated as follows: On column: TOSOH ODS-120T column ( Tosoh Corporation), eluent: acetonitrile / 0.6 mass% HClO 4 Under the conditions of water = 1 / 1 (vol / vol%), flow rate: 1.0 ml / min, sample amount: 300 μL, column temperature: 40°C, detection light: UV210 nm, HPLC was performed on standard substances with known octanol / water partition coefficients (heptanoic acid, octanoic acid, nonanoic acid and decanoic acid), and a calibration curve of each elution time and the known octanol / water partition coefficient was prepared. Based on the calibration curve, the elution time of HPLC in the sample solution was calculated.

[0594] Specific examples of the fluorinated surfactant include U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 142541, U.S. Patent Application Publication No. 2008 / 0015319, and U.S. Patent No. 3250808. Fluorinated surfactants described in Japanese Unexamined Patent Application No. 3,271,341, Japanese Unexamined Patent Application No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, Japanese Unexamined Patent Application 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.

[0595] Examples of the anionic fluorinated surfactant include the following general formula (N 0 ):

[0596] X n0 -Rf n0 -Y 0 (N0 )

[0597] (Where X n0 is H, Cl or and F. Rf n0 It is a chain, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H groups are replaced by F. The alkylene group may contain one or more ether bonds, and some of the H groups may be replaced by Cl. 0 is an anionic group).

[0598] Y 0 The anionic groups can be -COOM, -SO 2 M or -SO 3 M, can also be -COOM or -SO 3 M.

[0599] M is H, metal atom, NR 7 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

[0600] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li.

[0601] As R 7 , can be H or C 1-10 The organic group can also be H or C 1-4 The organic group can also be H or C 1-4 of alkyl.

[0602] M can be H, metal atom or NR 7 4 , or H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 4 , can also be H, Na, K, Li or NH 4 .

[0603] The above Rf n0 In the above formula (A), more than 50% of the H can be replaced by fluorine.

[0604] As the above general formula (N 0 ) can include:

[0605] The following general formula (N 1 ):

[0606] X n0 -(CF 2 ) m1 -Y0 (N 1 )

[0607] (Where X n0 is H, Cl and F, m1 is an integer from 3 to 15, Y 0 The compound represented by the following general formula (N 2 ):

[0608] R n1 -O-(CF(CF 3 )CF 2 O) m2 CFX n1 -Y 0 (N 2 )

[0609] (Where Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, and X n1 F or CF 3 , Y 0 The compound represented by the following general formula (N 3 ):

[0610] R n2 (CH 2 ) m3 -(Rf n3 ) q -Y 0 (N 3 )

[0611] (Where Rf n2 is a partially or completely fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y 0 The compound represented by the following general formula (N 4 ):

[0612] R n4 -O-(CY n1 Y n2 ) p CF 2 -Y 0 (N 4 )

[0613] (Where Rf n4 is a linear or branched partially or completely fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond and / or a chlorine atom, n1 and Y n2The same or different, H or F, p is 0 or 1, Y 0 The compound represented by the above-defined substance); and the general formula (N 5 ):

[0614] [Chemistry 19]

[0615]

[0616] (Where X n2 , X n3 and X n4 Rf may be the same or different and is H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond. n5 is a linear or branched partially or completely fluorinated alkylene group having 1 to 3 carbon atoms and may contain an ether bond, L is a connecting group, Y 0 is the substance defined above. n2 , X n3 , X n4 and Rf n5 The total number of carbon atoms is 18 or less).

[0617] As the above general formula (N 0 ), more specifically, a perfluorocarboxylic acid (I) represented by the following general formula (I), an ω-H perfluorocarboxylic acid (II) represented by the following general formula (II), a perfluoropolyether carboxylic acid (III) represented by the following general formula (III), a perfluoroalkyl alkylene carboxylic acid (IV) represented by the following general formula (IV), a perfluoroalkoxy fluorocarboxylic acid (V) represented by the following general formula (V), a perfluoroalkyl sulfonic acid (VI) represented by the following general formula (VI), an ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), a perfluoroalkyl alkylene sulfonic acid (VIII) represented by the following general formula (VIII), an alkyl alkylene carboxylic acid (IX) represented by the following general formula (IX), a fluorocarboxylic acid (X) represented by the following general formula (X), an alkoxy fluorosulfonic acid (XI) represented by the following general formula (XI), a compound (XII) represented by the following general formula (XII), a compound (XIII) represented by the following general formula (XIII), and the like.

[0618] The above perfluorocarboxylic acid (I) is represented by the following general formula (I):

[0619] F(CF 2 ) n1 COOM(I)

[0620] (where n1 is an integer from 3 to 14, M is H, a metal atom, NR 7 4, an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0621] The above-mentioned ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II):

[0622] H(CF 2 ) n2 COOM(II)

[0623] (wherein n2 is an integer of 4 to 15, and M is the substance defined above).

[0624] The above-mentioned perfluoropolyether carboxylic acid (III) is represented by the following general formula (III):

[0625] R 1 -O-(CF(CF 3 )CF 2 O) n3 CF(CF 3 )COOM(III)

[0626] (Where Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is the substance defined above).

[0627] The above perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV):

[0628] R 2 (CH 2 ) n4 R 3 COOM(IV)

[0629] (Where Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is the substance defined above).

[0630] The above alkoxy fluorocarboxylic acid (V) is represented by the following general formula (V):

[0631] R 4 -O-CY 1 Y 2 CF 2 -COOM(V)

[0632] (Where Rf 4 is a linear or branched partially or completely fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond and / or a chlorine atom, 1and Y 2 are the same or different, are H or F, and M is the substance defined above).

[0633] The above perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI):

[0634] F(CF 2 ) n5 SO 3 M(VI)

[0635] (wherein n5 is an integer of 3 to 14, and M is the substance defined above).

[0636] The above-mentioned ω-H perfluorosulfonic acid (VII) is represented by the following general formula (VII):

[0637] H(CF 2 ) n6 SO 3 M(VII)

[0638] (wherein n6 is an integer of 4 to 14, and M is the substance defined above).

[0639] The above perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII):

[0640] R 5 (CH 2 ) n7 SO 3 M(VIII)

[0641] (Where Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is the substance defined above).

[0642] The above alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX):

[0643] R 6 (CH 2 ) n8 COOM(IX)

[0644] (Where Rf 6 It is a linear or branched partially or completely fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer of 1 to 3, and M is the substance defined above).

[0645] The above fluorocarboxylic acid (X) is represented by the following general formula (X):

[0646] R 7 -O-Rf 8 -O-CF 2 -COOM(X)

[0647] (Where Rf 7 is a linear or branched partially or completely fluorinated alkyl group having 1 to 6 carbon atoms and which may contain an ether bond and / or a chlorine atom, Rf 8 is a linear or branched partially or completely fluorinated alkyl group having 1 to 6 carbon atoms, and M is the substance defined above).

[0648] The above alkoxy fluorosulfonic acid (XI) is represented by the following general formula (XI):

[0649] R 9 -O-CY 1 Y 2 CF 2 -SO 3 M(XI)

[0650] (Where Rf 9 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, which may be partially or completely fluorinated, 1 and Y 2 are the same or different, are H or F, and M is the substance defined above).

[0651] The above compound (XII) is represented by the following general formula (XII):

[0652] [Chemistry 20]

[0653]

[0654] (Where X 1 , X 2 and X 3 Rf may be the same or different and is H, F and a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and may contain an ether bond. 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a connecting group, Y 0 is an anionic group).

[0655] Y 0 Can be -COOM, -SO 2 M or -SO 3 M, can also be -SO 3 M or COOM (wherein M is the substance defined above).

[0656] Examples of L include a single bond and a partially or completely fluorinated alkylene group having 1 to 10 carbon atoms which may include an ether bond.

[0657] The above compound (XIII) is represented by the following general formula (XIII):

[0658] R 11 -O-(CF 2 CF(CF 3 )O) n9 (CF 2 O) n10 CF 2 COOM(XIII)

[0659] (Where Rf 11 is a fluorinated alkyl group having 1 to 5 carbon atoms and containing chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is the substance defined above). Examples of compound (XIII) include CF 2 ClO(CF 2 CF(CF 3 )O) n9 (CF 2 O) n10 CF 2 COONH 4 (mixture with an average molecular weight of 750, wherein n9 and n10 are the numbers defined above).

[0660] As described above, examples of the anionic fluorinated surfactant include carboxylic acid-based surfactants and sulfonic acid-based surfactants.

[0661] The fluorinated surfactant may be a single type of fluorinated surfactant or a mixture containing two or more types of fluorinated surfactants.

[0662] Examples of the fluorinated surfactant include compounds represented by the following formula: The fluorinated surfactant may be a mixture of these compounds: In one embodiment of the above polymerization, the fluorinated monomer is polymerized in the absence of a compound represented by the following formula.

[0663] F(CF 2 ) 7 COOM,

[0664] F(CF 2 ) 5 COOM,

[0665] H(CF 2 ) 6 COOM,

[0666] CF 3 O(CF 2 ) 3 OCHFCF 2 COOM,

[0667] C 3 F 7OCF(CF 3 )CF 2 OCF(CF 3 )COOM、

[0668] CF 3 CF 2 CF 2 OCF(CF 3 )COOM、

[0669] CF 3 CF 2 OCF 2 CF 2 OCF 2 COOM、

[0670] C 2 F 5 OCF(CF 3 )CF 2 OCF(CF 3 )COOM、

[0671] CF 3 OCF(CF 3 )CF 2 OCF(CF 3 )COOM、

[0672] CF 2 ClCF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 COOM、

[0673] CF 2 ClCF 2 CF 2 OCF 2 CF(CF 3 )OCF 2 COOM、

[0674] CF 2 ClCF(CF 3 )OCF(CF 3 )CF 2 OCF 2 COOM、

[0675] CF 2 ClCF(CF 3 )OCF 2 CF(CF 3 )OCF 2 COOM、

[0676] [Chemistry 21]

[0677]

[0678] (In each formula, M is H, metal atom, NR 7 4 , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 7 is H or an organic group. )

[0679] By the above polymerization, an aqueous dispersion containing the above fluorinated polymer can be obtained. The above fluorinated polymer is usually 8% to 50% by mass of the aqueous dispersion obtained by the above polymerization. In the above aqueous dispersion, the preferred lower limit of the concentration of the fluorinated polymer is 10% by mass, and the more preferred lower limit is 15% by mass, and the preferred upper limit is 40% by mass, and the more preferred upper limit is 35% by mass.

[0680] <Fluoropolymer>

[0681] Examples of the fluorine-containing polymer include TFE polymer (PTFE) in which the monomer having the largest molar fraction of monomers in the polymer (hereinafter referred to as "most abundant monomer") is TFE, VDF polymer in which the most abundant monomer is VDF, and CTFE polymer in which the most abundant monomer is CTFE.

[0682] The fluorinated polymer preferably has an ion exchange rate (IXR) higher than 53. The preferred fluorinated polymer has no ionic groups at all, or has a limited number of ionic groups that can bring about an ion exchange rate higher than about 100. The ion exchange rate of the preferred fluorinated polymer is preferably 1000 or higher, more preferably 2000 or higher, and further preferably 5000 or higher.

[0683] The TFE polymer may be a TFE homopolymer or a copolymer consisting of the following components: (1) TFE; (2) one or more fluorinated monomers other than TFE having 2 to 8 carbon atoms, particularly VDF, HFP or CTFE; and (3) other monomers. Examples of the above-mentioned (3) other monomers include fluoro(alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms; fluorodioxole; perfluoroalkylethylene; ω-hydrogenated perfluoroolefin; and the like.

[0684] The TFE polymer may also be a copolymer of TFE and one or more non-fluorine-containing monomers. Examples of the non-fluorine-containing monomers include olefins such as ethylene and propylene; vinyl esters; and vinyl ethers. The TFE polymer may also be a copolymer of TFE, one or more fluorine-containing monomers having 2 to 8 carbon atoms, and one or more non-fluorine-containing monomers.

[0685] The VDF polymer may be suitably a VDF homopolymer [PVDF] or a copolymer consisting of: (1) VDF; (2) one or more fluoroolefins other than VDF having 2 to 8 carbon atoms, in particular TFE, HFP or CTFE; and (3) a perfluoro(alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, in particular 1 to 3 carbon atoms; etc.

[0686] The CTFE polymer may be a CTFE homopolymer or a copolymer consisting of: (1) CTFE; (2) one or more fluoroolefins other than CTFE having 2 to 8 carbon atoms, particularly TFE or HFP; and (3) a perfluoro(alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms.

[0687] The CTFE polymer may be a copolymer of CTFE and one or more non-fluorine-containing monomers. Examples of the non-fluorine-containing monomers include olefins such as ethylene and propylene; vinyl esters; and vinyl ethers.

[0688] The fluorine-containing polymers may be glassy, ​​plastic or elastomeric. These materials are amorphous or partially crystalline and can be subjected to compression sintering, melt processing or non-melt processing.

[0689] The production method of the present invention can suitably produce, for example, the following substances: (I) tetrafluoroethylene polymer [TFE polymer (PTFE)] as a non-melt-processable fluororesin, (II) ethylene / TFE copolymer [ETFE], TFE / HFP copolymer [FEP], TFE / perfluoro(alkyl vinyl ether) copolymer [PFA, MFA, etc.], TFE / perfluoroallyl ether copolymer, TFE / VDF copolymer, and electrolyte polymer precursor as melt-processable fluororesins, (III) TFE / propylene copolymer, TFE / propylene / third monomer copolymer (the third monomer is VDF, HFP, CTFE, fluoroalkyl vinyl ether, etc.), and copolymer composed of TFE and fluoroalkyl vinyl ether as fluororubber; HFP / ethylene copolymer, HFP / ethylene / TFE copolymer; PVDF; thermoplastic elastomers such as VDF / HFP copolymer, HFP / ethylene copolymer, and VDF / TFE / HFP copolymer; and fluorine-containing segmented polymers described in Japanese Patent Publication No. 61-49327; and the like.

[0690] As the above-mentioned fluorine-containing polymer, a fluororesin is preferred, among which a fluororesin having a fluorine substitution rate of 50% or more as calculated by the following formula is more preferred, a fluororesin having a fluorine substitution rate of more than 50% is further preferred, a fluororesin having a fluorine substitution rate of 55% or more is still more preferred, a fluororesin having a fluorine substitution rate of 60% or more is still more preferred, a fluororesin having a fluorine substitution rate of 75% or more is still more preferred, a fluororesin having a fluorine substitution rate of 80% or more is particularly preferred, and a fluororesin having a fluorine substitution rate of 90% to 100%, i.e., a perfluororesin, is most preferred.

[0691] (Mode)

[0692] Fluorine substitution rate (%) = (the number of fluorine atoms bonded to the carbon atoms constituting the fluorine-containing polymer) / ((the number of hydrogen atoms bonded to the carbon atoms constituting the fluorine-containing polymer) + (the number of fluorine atoms and chlorine atoms bonded to the carbon atoms constituting the fluorine-containing polymer)) × 100

[0693] As the perfluororesin, a fluororesin having a fluorine substitution rate of 95% to 100% is more preferred, PTFE, FEP, and PFA are further preferred, and PTFE is particularly preferred.

[0694] The above-mentioned fluoropolymer can have a core-shell structure. As the fluoropolymer with the core-shell structure, for example, a modified PTFE that comprises a core of a high molecular weight PTFE and a shell of a lower molecular weight PTFE or modified PTFE in a particle can be enumerated. As such a modified PTFE, for example, the PTFE described in writing in the Japanese Patent Table 2005-527652 communique can be enumerated.

[0695] As the core-shell structure, for example, the following structures can be adopted.

[0696] Core: TFE homopolymer Shell: TFE homopolymer

[0697] Core: modified PTFE Shell: TFE homopolymer

[0698] Core: Modified PTFE Shell: Modified PTFE

[0699] Core: TFE homopolymer Shell: Modified PTFE

[0700] Core: low molecular weight PTFE Shell: high molecular weight PTFE

[0701] Core: High molecular weight PTFE Shell: Low molecular weight PTFE

[0702] In the fluorinated polymer having the core-shell structure, the lower limit of the ratio of the core is preferably 0.5 mass%, more preferably 1.0 mass%, further preferably 3.0 mass%, particularly preferably 5.0 mass%, and most preferably 10.0 mass%. The upper limit of the ratio of the core is preferably 99.5 mass%, more preferably 99.0 mass%, further preferably 98.0 mass%, further more preferably 97.0 mass%, particularly preferably 95.0 mass%, and most preferably 90.0 mass%.

[0703] In the fluorinated polymer having the core-shell structure, the lower limit of the ratio of the shell is preferably 0.5 mass%, more preferably 1.0 mass%, further preferably 3.0 mass%, particularly preferably 5.0 mass%, and most preferably 10.0 mass%. The upper limit of the ratio of the shell is preferably 99.5 mass%, more preferably 99.0 mass%, further preferably 98.0 mass%, further more preferably 97.0 mass%, particularly preferably 95.0 mass%, and most preferably 90.0 mass%.

[0704] In the fluoropolymer having the core-shell structure, the core or the shell may be formed into two or more layers. For example, the fluoropolymer may be a three-layer structure having a core center portion of modified PTFE, a core outer layer portion of a TFE homopolymer, and a shell of modified PTFE.

[0705] Examples of the fluorinated polymer having a core-shell structure include a fluorinated polymer in which one particle of the fluorinated polymer has a plurality of cores.

[0706] The above-mentioned (I) non-melt-processable fluororesin, (II) melt-processable fluororesin and (III) fluororubber suitably produced by the production method of the present invention are preferably produced as follows.

[0707] (I) Non-melt-processable fluororesins

[0708] In the production method of the present invention, the polymerization of TFE is usually carried out at a polymerization temperature of 10°C to 150°C and a polymerization pressure of 0.05MPaG to 5MPaG. For example, the polymerization temperature is more preferably 30°C or more, and more preferably 50°C or more. In addition, it is more preferably 120°C or less, and more preferably 100°C or less. In addition, the polymerization pressure is more preferably 0.3MPaG or more, and more preferably 0.5MPaG or more, and more preferably 5.0MPaG or less, and more preferably 3.0MPaG or less. In particular, from the aspect of increasing the amount of fluorinated polymer obtained, it is preferably 1.0MPaG or more, more preferably 1.2MPaG or more, more preferably 1.5MPaG or more, and more preferably 2.0MPaG or more.

[0709] In one embodiment, regarding the above-mentioned polymerization, pure water is added to a pressure-resistant reaction vessel equipped with a stirrer, and TFE is added after deoxygenation to make it reach a predetermined temperature, and a polymerization initiator is added to initiate the reaction. When the pressure decreases as the reaction proceeds, additional TFE is continuously or intermittently supplied to maintain the initial pressure. When a predetermined amount of TFE is supplied, the supply is stopped, the TFE in the reaction vessel is purged, the temperature is restored to room temperature, and the reaction is terminated. In order to prevent the pressure from decreasing, additional TFE can be continuously or intermittently supplied.

[0710] In the production of the above-mentioned TFE polymer (PTFE), various known modified monomers may also be used in combination. In the present invention, the above-mentioned TFE polymer is a concept that includes not only TFE homopolymers but also non-melt-processable substances (hereinafter referred to as "modified PTFE") that are copolymers of TFE and modified monomers.

[0711] The modifying monomer is not particularly limited as long as it is copolymerizable with TFE, and examples thereof include fluorine-containing monomers and non-fluorine-containing monomers. The modifying monomer used may be one kind or two or more kinds.

[0712] The non-fluorine-containing monomer is not particularly limited, and examples thereof include the following:

[0713] CH 2 =CR Q1 -LR Q2

[0714] (Where R Q1 represents a hydrogen atom or an alkyl group. L represents a single bond, -CO-O-*, -O-CO-* or -O-. * represents the same Q2 The bonding position of R Q2 represents a hydrogen atom, an alkyl group or a nitrile group).

[0715] Examples of the non-fluorine-containing monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, vinyl methacrylate, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, ethyl vinyl ether, and cyclohexyl vinyl ether. Among the non-fluorine-containing monomer, butyl methacrylate, vinyl acetate, and acrylic acid are preferred.

[0716] Examples of the fluorine-containing monomer include perfluoroolefins such as hexafluoropropylene [HFP]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as chlorotrifluoroethylene; perfluorovinyl ether; (perfluoroalkyl)ethylene; and perfluoroallyl ether.

[0717] The perfluorovinyl ether is not particularly limited, and examples thereof include those of the general formula (A):

[0718] CF 2 =CF-ORf(A)

[0719] (wherein Rf represents a perfluoro organic group) and the like. In the present invention, the above-mentioned "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen.

[0720] Examples of the perfluorovinyl ether include perfluoro(alkyl vinyl ether) [PAVE] wherein Rf in the general formula (A) is a perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

[0721] Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0722] As the perfluorovinyl ether, further examples include monomers wherein Rf in the general formula (A) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:

[0723] [Chemistry 22]

[0724]

[0725] (wherein m represents 0 or an integer of 1 to 4) and Rf is the following formula:

[0726] [Chemistry 23]

[0727]

[0728] (wherein n represents an integer of 1 to 4) and the like.

[0729] Examples of hydrogen-containing fluoroolefins include CH 2 =CF 2 CFH=CH 2 CFH=CF 2 CF 2 =CFCF 3 , CH 2 =CFCF 3 , CH 2 =CHCF 3 、CHF=CHCF 3 (E body), CHF=CHCF 3 (Z body) etc.

[0730] The (perfluoroalkyl)ethylene (PFAE) is not particularly limited, and examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.

[0731] Examples of the perfluoroallyl ether include

[0732] General formula: CF 2 =CF-CF 2 -ORf

[0733] (wherein Rf represents a perfluoro organic group).

[0734] Rf in the above general formula is the same as Rf in general formula (A). As Rf, a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms is preferred. As perfluoroallyl ether, a group selected from CF 2 =CF-CF 2 -O-CF 3 CF 2 =CF-CF 2 -OC 2 F 5 CF 2 =CF-CF 2 -OC 3 F 7 and CF 2 =CF-CF 2 -OC 4 F 9 At least one of the group consisting of, more preferably selected from CF 2 =CF-CF 2 -OC 2 F 5 CF 2 =CF-CF 2 -OC3 F 7 and CF 2 =CF-CF 2 -OC 4 F 9 At least one of the group consisting of, more preferably CF 2 =CF-CF 2 -O-CF 2 CF 2 CF 3 .

[0735] Preferred examples of the modified monomer include a modified monomer (3) having a monomer reactivity ratio of 0.1 to 8. The presence of the modified monomer (3) can provide PTFE particles having a small particle size and an aqueous dispersion having high dispersion stability.

[0736] Here, the monomer reactivity ratio in the copolymerization with TFE is a value obtained as follows: when the growth free radical is smaller than the repeating unit based on TFE, the rate constant when the growth free radical reacts with TFE is divided by the rate constant when the growth free radical reacts with the modified monomer, and the obtained value is the above-mentioned monomer reactivity ratio. The lower the value, the higher the reactivity of the modified monomer with TFE. The monomer reactivity ratio can be calculated as follows: copolymerize TFE and the modified monomer, find the composition of the generated polymer immediately after the start, and calculate it by the Fineman-Ross formula.

[0737] The copolymerization is carried out in a stainless steel autoclave with an internal volume of 6.0 L using 3600 g of deionized degassed water, 1000 mass ppm of ammonium perfluorooctanoate relative to the water, and 100 g of paraffin at a pressure of 0.78 MPaG and a temperature of 70°C. 0.05 g, 0.1 g, 0.2 g, 0.5 g, and 1.0 g of the modified monomer are added to the reactor respectively, and 0.072 g of ammonium persulfate (20 mass ppm relative to water) is added. In order to maintain a polymerization pressure of 0.78 MPaG, TFE is continuously supplied. When the TFE feed reaches 1000 g, stirring is stopped and depressurization is performed until the reactor reaches atmospheric pressure. After cooling, paraffin is separated to obtain an aqueous dispersion containing the generated polymer. The aqueous dispersion is stirred to precipitate the generated polymer and dried at 150°C. The composition of the resulting polymer is calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

[0738] The modified monomer (3) having a monomer reactivity ratio of 0.1 to 8 is preferably at least one selected from the group consisting of modified monomers represented by formulas (3a) to (3d).

[0739] CH 2 =CH-Rf1 (3a)

[0740] (Where Rf 1 It is a perfluoroalkyl group having 1 to 10 carbon atoms. )

[0741] CF 2 =CF-O-Rf 2 (3b)

[0742] (Where Rf 2 It is a perfluoroalkyl group having 1 to 2 carbon atoms. )

[0743] CF 2 =CF-O-(CF 2 ) n CF=CF 2 (3c)

[0744] (In the formula, n is 1 or 2.)

[0745] [Chemistry 24]

[0746]

[0747] (Where X 3 and X 4 is F, Cl or methoxy, and Y is of the formula Y1 or Y2.)

[0748] [Chemistry 25]

[0749]

[0750] (In formula Y2, Z and Z' are F or a fluorinated alkyl group having 1 to 3 carbon atoms.)

[0751] The content of the modified monomer (3) unit is preferably in the range of 0.00001% to 1.0% by mass relative to the total polymerized units of PTFE. As the lower limit, it is more preferably 0.0001% by mass, more preferably 0.0005% by mass, further preferably 0.001% by mass, and further more preferably 0.005% by mass. As the upper limit, it is 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, 0.08% by mass, 0.05% by mass, 0.01% by mass in a preferred order.

[0752] As above-mentioned modified monomer, owing to can obtain the aqueous dispersion liquid of the average primary particle diameter of primary particle little, the aspect ratio of primary particle little, excellent stability, thus preferably selected from at least one in the group of the modified monomer composition of hexafluoropropylene, trifluorochloroethylene, vinylidene fluoride, perfluor (alkyl vinyl ether), (perfluoroalkyl) ethylene, ethylene and the functional group that can pass through free radical polymerization and hydrophilic group.By using above-mentioned modified monomer, can obtain the aqueous dispersion liquid of the PTFE that average primary particle diameter is little, the aspect ratio of primary particle is little, excellent dispersion stability.In addition, can obtain the aqueous dispersion liquid that does not precipitate polymer few.

[0753] From the viewpoint of reactivity with TFE, the modifying monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether) and (perfluoroalkyl)ethylene.

[0754] More preferably, it contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), (perfluorobutyl)ethylene, (perfluorohexyl)ethylene, and (perfluorooctyl)ethylene.

[0755] The total amount of the above-mentioned hexafluoropropylene unit, perfluoro (alkyl vinyl ether) unit and (perfluoroalkyl) ethylene unit is preferably in the range of 0.00001 mass % to 1 mass % relative to the total polymerized units of PTFE. As the lower limit of the above-mentioned total amount, it is more preferably 0.0001 mass %, more preferably 0.0005 mass %, further preferably 0.001 mass %, further preferably 0.005 mass %. As the upper limit, it is 0.80 mass %, 0.70 mass %, 0.50 mass %, 0.40 mass %, 0.30 mass %, 0.20 mass %, 0.15 mass %, 0.10 mass %, 0.08 mass %, 0.05 mass %, 0.01 mass %.

[0756] The above-mentioned modified monomer also preferably includes a modified monomer having a functional group capable of a radical polymerization reaction and a hydrophilic group (hereinafter referred to as "modified monomer (A)").

[0757] The presence of the modified monomer (A) can provide PTFE particles with a small primary particle size, and an aqueous dispersion with high dispersion stability. In addition, the amount of unprecipitated polymer can be reduced. Furthermore, the aspect ratio of the primary particles can be reduced.

[0758] The amount of the modified monomer (A) is preferably an amount exceeding an amount equivalent to 0.1 mass ppm of the aqueous medium, more preferably an amount exceeding 0.5 mass ppm, further preferably an amount exceeding 1.0 mass ppm, and further more preferably 5 mass ppm or more, particularly preferably 10 mass ppm or more. If the amount of the modified monomer (A) is too small, the average primary particle size of the obtained PTFE may not be reduced.

[0759] The amount of the modified monomer (A) may be within the above range, and the upper limit may be 5000 ppm by mass, for example. In addition, in the above production method, in order to improve the stability of the aqueous dispersion during or after the reaction, the modified monomer (A) may be added to the system during the reaction.

[0760] The modified monomer (A) has high water solubility. Therefore, even if unreacted modified monomer (A) remains in the aqueous dispersion, it can be easily removed in the concentration step or the precipitation / washing step.

[0761] The modified monomer (A) is introduced into the resulting polymer during the polymerization process. However, since the concentration of the modified monomer (A) in the polymerization system is low and the amount introduced into the polymer is small, there is no problem of reduced heat resistance of PTFE or coloration after firing.

[0762] Examples of the hydrophilic group in the modified monomer (A) include -NH 2 ,-PO 3 M, -OPO 3 M, -SO 3 M, -OSO 3 M, -COOM (in each formula, M is H, metal atom, NR 7y 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7y H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring). As the above-mentioned hydrophilic group, -SO 3 M or -COOM. As R 7y The organic group in is preferably an alkyl group. 7y , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 of alkyl.

[0763] Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0764] Examples of the "functional group capable of free radical polymerization" in the modified monomer (A) include groups having ethylenically unsaturated bonds such as vinyl and allyl groups. The group having ethylenically unsaturated bonds can be represented by the following formula:

[0765] CX e X g =CX f R-

[0766] (Where X e , X f and X g Each independently is F, Cl, H, CF 3 CF 2 H.CFH 2 or CH 3 ; R is a linking group). As the linking group of R, there can be mentioned R a A preferred connecting group is -CH=CH 2 、-CF=CH 2、 -CH=CF 2、 -CF=CF 2 、-CH 2 -CH=CH 2 , -CF 2 -CF=CH 2 , -CF 2 -CF=CF 2 、-(C=O)-CH=CH 2 、-(C=O)-CF=CH 2 、-(C=O)-CH=CF 2 , -(C=O)-CF=CF 2 、-(C=O)-C(CH 3 )=CH 2 , -(C=O)-C(CF 3 )=CH 2 、-(C=O)-C(CH 3 )=CF 2 , -(C=O)-C(CF 3 )=CF 2 、-O-CH 2 -CH=CH 2 、-O-CF 2 -CF=CH 2 、-O-CH 2 -CH=CF 2 、-O-CF 2 -CF=CF 2 etc. having unsaturated bonds.

[0767] Since the modified monomer (A) has a functional group capable of free radical polymerization, if used in the polymerization, it reacts with the fluorinated monomer in the early stage of the polymerization reaction, and it is presumed that the hydrophilic group derived from the modified monomer (A) can form particles with high stability. Therefore, if the polymerization is carried out in the presence of the modified monomer (A), it is thought that the number of particles increases.

[0768] In the above polymerization, the above-mentioned modified monomer (A) may be present alone or in combination of two or more.

[0769] In the above-mentioned polymerization, a compound having an unsaturated bond can be used as the above-mentioned modified monomer (A).

[0770] The modified monomer (A) is preferably of the general formula (4):

[0771] CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4)

[0772] (Where X i , X j and X k Each independently is F, Cl, H or CF 3 ; Y 3 is a hydrophilic group; R a is a connecting group; Z 1 and Z 2 Each independently is H, F or CF 3 , k is 0 or 1).

[0773] Examples of the hydrophilic group include -NH 2 ,-PO 3 M, -OPO 3 M, -SO 3 M, -OSO 3 M, -COOM (in each formula, M is H, metal atom, NR 7y 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7y H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring). As the above-mentioned hydrophilic group, -SO 3 M or -COOM. As R 7y The organic group in is preferably an alkyl group. 7y , preferably H or C1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 The metal atom may be a monovalent or divalent metal atom, and may be an alkali metal (Group 1) or an alkaline earth metal (Group 2). Preferably, Na, K or Li is used.

[0774] By using the modified monomer (A), an aqueous dispersion having a smaller average primary particle size and better stability can be obtained, and the aspect ratio of the primary particles can be further reduced.

[0775] The above R a is a linking group. In the present invention, "linking group" refers to a divalent linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. The upper limit is not limited, for example, it may be 100 or less, or 50 or less.

[0776] The linking group may be a chain or branched chain, a cyclic or acyclic structure, saturated or unsaturated, substituted or unsubstituted, and may contain one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as desired, and may contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, carbamate, urea and carbamate as desired. The linking group does not contain carbon atoms and may be a chain heteroatom such as oxygen, sulfur or nitrogen.

[0777] The above R a Preferred are, for example, chain heteroatoms such as oxygen, sulfur, and nitrogen, or divalent organic groups.

[0778] R a In the case of 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. a It may be in the form of a chain or a branched chain, or in the form of a ring or an acyclic ring. a Functional groups (eg, ester, ether, ketone, amine, halide, etc.) may be included.

[0779] In addition, R a It may be a non-fluorinated divalent organic group or a partially fluorinated or perfluorinated divalent organic group.

[0780] As R a, and can be, for example: a hydrocarbon group in which no fluorine atoms are bonded to the carbon atom; a hydrocarbon group in which a part of the hydrogen atoms bonded to the carbon atom are substituted by fluorine atoms; a hydrocarbon group in which all the hydrogen atoms bonded to the carbon atom are substituted by fluorine atoms; a hydrocarbon group containing -(C=O)-, -(C=O)-O- or -(C=O)-, which may contain oxygen atoms, double bonds, and functional groups.

[0781] R a Preferably, it is a hydrocarbon group having 1 to 100 carbon atoms which may contain -(C=O)-, -(C=O)-O- or an ether bond and may contain a carbonyl group, and a part or all of the hydrogen atoms bonded to the carbon atoms in the hydrocarbon group may be substituted with fluorine.

[0782] As R a , preferably selected from -(CH 2 ) a -、-(CF 2 ) a -、-O-(CF 2 ) a -、-(CF 2 ) a -O-(CF 2 ) b -、-O(CF 2 ) a -O-(CF 2 ) b -、-(CF 2 ) a -[O-(CF 2 ) b ] c -、-O(CF 2 ) a -[O-(CF 2 ) b ] c -、-[(CF 2 ) a -O] b -[(CF 2 ) c -O] d -、-O[(CF 2 ) a -O] b -[(CF 2 ) c -O] d -、-O-[CF 2 CF(CF 3 )O] a -(CF 2 ) b -, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2 ) a -、-(C=O)-(CF 2 ) a -、-(C=O)-O-(CH 2 ) a -、-(C=O)-O-(CF 2 ) a -、-(C=O)-[(CH 2 ) a -O] b -、-(C=O)-[(CF 2 ) a -O] b -、-(C=O)-O[(CH 2 ) a -O] b -、-(C=O)-O[(CF 2 ) a -O] b -、-(C=O)-O[(CH 2 ) a -O] b -(CH 2 ) c -、-(C=O)-O[(CF 2 ) a -O] b -(CF 2 ) c -、-(C=O)-(CH 2 ) a -O-(CH 2 ) b -、-(C=O)-(CF 2 ) a -O-(CF 2 ) b -、-(C=O)-O-(CH 2 ) a -O-(CH 2 ) b -、-(C=O)-O-(CF 2 ) a -O-(CF 2 ) b -、-(C=O)-OC 6 H 4 - and at least one of their combinations.

[0783] In the formula, a, b, c and d are independently at least 1. a, b, c and d can independently be 2 or more, 3 or more, 4 or more, 10 or more, or 20 or more. The upper limit of a, b, c and d is, for example, 100.

[0784] As R a A preferred specific example is -CF 2 -O-, -CF 2 -O-CF 2 -、-CF 2 -O-CH 2 -、-CF 2 -O-CH 2 CF 2 -、-CF 2 -O-CF 2 CF 2 -、-CF 2 -O-CF 2 CH 2 -、-CF 2 -O-CF 2 CF 2 CH 2 -、-CF 2 -O-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -、-CF 2 -O-CF(CF 3 )CF 2 -O-, -CF 2 -O-CF(CF 3 )CH 2 -, -(C=O)-, -(C=O)-O-, -(C=O)-(CH 2 )-、-(C=O)-(CF 2 )-、-(C=O)-O-(CH 2 )-、-(C=O)-O-(CF 2 )-、-(C=O)-[(CH 2 ) 2 -O] n -、-(C=O)-[(CF 2 ) 2 -O] n -、-(C=O)-O[(CH 2 ) 2 -O] n -、-(C=O)-O[(CF 2 ) 2 -O]n -, -(C=O)-O[(CH 2 ) 2 -O] n -(CH 2 )-, -(C=O)-O[(CF 2 ) 2 -O] n -(CF 2 )-, -(C=O)-(CH 2 ) 2 -O-(CH 2 )-, -(C=O)-(CF 2 ) 2 -O-(CF 2 )-, -(C=O)-O-(CH 2 ) 2 -O-(CH 2 )-, -(C=O)-O-(CF 2 ) 2 -O-(CF 2 )-, -(C=O)-O-C 6 H 4 - etc. Among them, specifically, the above R a is preferably -CF 2 -O-, -CF 2 -O-CF 2 -, -CF 2 -O-CF 2 CF 2 -, -CF 2 -O-CF(CF 3 )-, -CF 2 -O-CF(CF 3 )CF 2 -, -CF 2 -O-CF(CF 3 )CF 2 -O-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH 2 )-, -(C=O)-O-(CH 2 )-, -(C=O)-O[(CH 2 ) 2 -O] n -, -(C=O)-O[(CH 2 ) 2 -O] n -(CH 2 )-, -(C=O)-(CH 2 ) 2 -O-(CH 2)-, or -(C=O)-O-C 6 H 4 -.

[0785] In the above formula, n is an integer from 1 to 10.

[0786] As -R in general formula (4) a -(CZ 1 Z 2 ) k -, preferably -CF 2 -O-CF 2 -, -CF 2 -O-CF(CF 3 )-, -CF 2 -O-C(CF 3 ) 2 -, -CF 2 -O-CF 2 -CF 2 -, -CF 2 -O-CF 2 -CF(CF 3 )-, -CF 2 -O-CF 2 -C(CF 3 ) 2 -, -CF 2 -O-CF 2 CF 2 -CF 2 -, -CF 2 -O-CF 2 CF 2 -CF(CF 3 )-, -CF 2 -O-CF 2 CF 2 -C(CF 3 ) 2 -, -CF 2 -O-CF(CF 3 )-CF 2 -, -CF 2 -O-CF(CF 3 )-CF(CF 3 )-, -CF 2 -O-CF(CF 3 )-C(CF 3 ) 2 -, -CF 2 -O-CF(CF 3 )-CF 2 -, -CF 2 -O-CF(CF 3 )-CF(CF3 )-、-CF 2 -O-CF(CF 3 )-C(CF 3 ) 2 -、-CF 2 -O-CF(CF 3 )CF 2 -CF 2 -、-CF 2 -O-CF(CF 3 )CF 2 -CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -C(CF 3 ) 2 -、-CF 2 -O-CF(CF 3 )CF 2 -O-CF 2 -、-CF 2 -O-CF(CF 3 )CF 2 -O-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -O-C(CF 3 ) 2 -、-(C=O)-、-(C=O)-O-、-(C=O)-(CH 2 )-、-(C=O)-(CF 2 )-、-(C=O)-O-(CH 2 )-、-(C=O)-O-(CF 2 )-、-(C=O)-[(CH 2 ) 2 -O] n -(CH 2 )-、-(C=O)-[(CF 2 ) 2 -O] n -(CF 2 )-、-(C=O)-[(CH 2 ) 2 -O] n -(CH 2 )-(CH 2 )-、-(C=O)-[(CF 2 ) 2 -O] n -(CF 2 )-(CF2 )-, -(C=O)-O[(CH 2 ) 2 -O] n -(CF 2 )-, -(C=O)-O[(CH 2 ) 2 -O] n -(CH 2 )-(CH 2 )-, -(C=O)-O[(CF 2 ) 2 -O] n -(CF 2 )-, -(C=O)-O[(CF 2 ) 2 -O] n -(CF 2 )-(CF 2 )-, -(C=O)-(CH 2 ) 2 -O-(CH 2 )-(CH 2 )-, -(C=O)-(CF 2 ) 2 -O-(CF 2 )-(CF 2 )-, -(C=O)-O-(CH 2 ) 2 -O-(CH 2 )-(CH 2 )-, -(C=O)-O-(CF 2 ) 2 -O-(CF 2 )-(CF 2 )-, -(C=O)-O-(CH 2 ) 2 -O-(CH 2 )-C(CF 3 ) 2 -., -(C=O)-O-(CF 2 ) 2 -O-(CF 2 )-C(CF 3 ) 2 -., or -(C=O)-O-C 6 H 4 -C(CF 3 ) 2 -, more preferably -CF 2 -O-CF(CF 3 )-., -CF 2 -O-CF 2-CF(CF 3 )-、-CF 2 -O-CF 2 CF 2 -CF(CF 3 )-、-CF 2 -O-CF(CF 3 )-CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -CF(CF 3 )-、-CF 2 -O-CF(CF 3 )CF 2 -O-CF(CF 3 )-, -(C=O)-, -(C=O)-O-(CH 2 )-、-(C=O)-O-(CH 2 )-(CH 2 )-、-(C=O)-O[(CH 2 ) 2 -O] n -(CH 2 )-(CH 2 )-、-(C=O)-O-(CH 2 ) 2 -O-(CH 2 )-C(CF 3 ) 2 -, or -(C=O)-OC 6 H 4 -C(CF 3 ) 2 -.

[0787] In the above formula, n is an integer of 1-10.

[0788] Specific examples of the compound represented by the general formula (4) include:

[0789] [Chemistry 26]

[0790]

[0791] (Where X j and Y 3 Same as above. n is an integer from 1 to 10) and the like.

[0792] As R a , preferably general formula (r1):

[0793] -(C=O) h -(O) i -CF2 -O-(CX 6 2 ) e -{O-CF(CF 3 )} f -(O) g -(r1)

[0794] (Where X 6 Each independently is H, F or CF 3 , e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1), and the general formula (r2) is also preferred:

[0795] -(C=O) h -(O) i -CF 2 -O-(CX 7 2 ) e -(O) g -(r2)

[0796] (Where X 7 Each independently is H, F or CF 3 , e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1).

[0797] As -R in the general formula (4) a -(CZ 1 Z 2 ) k -, the following formula (t1) is also preferred:

[0798] -(C=O) h -(O) i -CF 2 -O-(CX 6 2 ) e -{O-CF(CF 3 )} f -(O) g -CZ 1 Z 2 -(t1)

[0799] (Where X 6 Each independently is H, F or CF 3 , e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, Z 1 and Z 2 Each independently is F or CF 3 ) is a divalent group represented by formula (t1), wherein Z 1 and Z2 More preferably, one is F and the other is CF 3 .

[0800] In the general formula (4), -R a -(CZ 1 Z 2 ) k -, the following formula (t2) is also preferred:

[0801] -(C=O) h -(O) i -CF 2 -O-(CX 7 2 ) e -(O) g -CZ 1 Z 2 -(t2)

[0802] (Where X 7 Each independently is H, F or CF 3 , e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, Z 1 and Z 2 Each independently is F or CF 3 ) is a divalent group represented by formula (t2), wherein Z 1 and Z 2 More preferably, one is F and the other is CF 3 .

[0803] The compound represented by the general formula (4) also preferably has a hydrophilic group (Y 3 ) has a CF bond and does not have a CH bond. That is, in the general formula (4), preferably X i , X j and X k All are F, R a The perfluoroalkylene group may have 1 or more carbon atoms, and the perfluoroalkylene group may be any of a chain or branched chain, cyclic or acyclic, and may contain at least one chain heteroatom. The perfluoroalkylene group may have 2 to 20 carbon atoms, or 4 to 18 carbon atoms.

[0804] The compound represented by the general formula (4) may also be partially fluorinated. That is, the compound represented by the general formula (4) also preferably has, in addition to the hydrophilic group (Y 3 ) has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0805] The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4a).

[0806] CF2 =CF-O-Rf 0 -Y 3 (4a)

[0807] (Where Y 3 is a hydrophilic group, Rf 0 It is perfluorinated and may be chain or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and is a perfluorinated divalent linking group that optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen.

[0808] The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4b).

[0809] CH 2 =CH-O-Rf 0 -Y 3 (4b)

[0810] (Where Y 3 is a hydrophilic group, Rf 0 is a perfluorinated divalent linking group defined by formula (4a).

[0811] In the general formula (4), Y 3 For-OSO 3 M is one of the preferred methods. 3 For-OSO 3 In the case of M, examples of the compound represented by the general formula (4) include CF 2 =CF(OCF 2 CF 2 CH 2 OSO 3 M), CH 2 =CH((CF 2 ) 4 CH 2 OSO 3 M), CF 2 =CF(O(CF 2 ) 4 CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CH 2 OSO 3M), CH 2 =CH((CF 2 ) 4 CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OSO 3 M), CH 2 =CH(CF 2 CF 2 CH 2 OSO 3 M), CF 2 =CF(OCF 2 CF 2 CF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OSO 3 M) etc. In the above formula, M is the same as above.

[0812] In the general formula (4), Y 3 For-SO 3 M is also one of the preferred methods. 3 For-SO 3 In the case of M, examples of the compound represented by the general formula (4) include CF 2 =CF(OCF 2 CF 2 SO 3 M), CF 2 =CF(O(CF 2 ) 4 SO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )SO 3 M), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 SO 3 M), CH 2 =CH(CF 2 CF 2 SO 3 M), CF 2=CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CF 2 CF 2 SO 3 M), CH 2 =CH((CF 2 ) 4 SO 3 M), CH 2 =CH((CF 2 ) 3 SO 3 M) etc. In the above formula, M is the same as above.

[0813] In the general formula (4), Y 3 -COOM is also one of the preferred methods. 3 In the case of -COOM, examples of the compound represented by the general formula (4) include CF 2 =CF(OCF 2 CF 2 COOM), CF 2 =CF(OCF 2 CF 2 CF 2 COOM), CF 2 =CF(O(CF 2 ) 5 COOM), CF 2 =CF(OCF 2 CF(CF 3 )COOM)、CF 2 =CF(OCF 2 CF(CF 3 )O(CF 2 ) n COOM)(n greater than 1), CH 2 =CH(CF 2 CF 2 COOM), CH 2 =CH((CF 2 ) 4 COOM), CH 2 =CH((CF 2 ) 3 COOM), CF 2 =CF(OCF 2 CF 2 SO 2 NR'CH 2 COOM), CF 2 =CF(O(CF 2 )4 SO 2 NR'CH 2 COOM), CF 2 =CF(OCF 2 CF(CF 3 )SO 2 NR'CH 2 COOM), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 NR'CH 2 COOM)、CH 2 =CH(CF 2 CF 2 SO 2 NR'CH 2 COOM), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CF 2 CF 2 SO 2 NR'CH 2 COOM)、CH 2 =CH((CF 2 ) 4 SO 2 NR'CH 2 COOM)、CH 2 =CH((CF 2 ) 3 SO 2 NR'CH 2 COOM) etc. In the above formula, R' is H or C 1-4 The alkyl group and M are the same as described above.

[0814] In the general formula (4), Y 3 OPO 3 M or -OP(O)(OM) 2 It is also one of the preferred methods. 3 OPO 3 M or -OP(O)(OM) 2 In the case of 2 =CF(OCF 2 CF 2 CH 2 OP(O)(OM) 2 ), CF 2=CF(O(CF 2 ) 4 CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OP(O)(OM) 2 ), CF 2 =CF(OCF 2 CF 2 CF 2 CF 2 SO 2 N(CH 3 )CH 2 CH 2 OP(O)(OM) 2 ), CH 2 =CH(CF 2 CF 2 CH 2 OP(O)(OM) 2 , CH 2 =CH((CF 2 ) 4 CH 2 OP(O)(OM) 2 ), CH 2 =CH((CF 2 ) 3 CH 2 OP(O)(OM) 2 ) etc. In the above formula, M is the same as above.

[0815] In the general formula (4), Y 3 For-PO 3 M or -P(O)(OM) 2 It is also one of the preferred methods. 3 For-PO 3M or -P(O)(OM) 2 In the case of 2 =CF(OCF 2 CF 2 P(O)(OM) 2 ), CF 2 =CF(O(CF 2 ) 4 P(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )P(O)(OM) 2 ), CF 2 =CF(OCF 2 CF(CF 3 )OCF 2 CF 2 P(O)(OM) 2 ), CH 2 =CH(CF 2 CF 2 P(O)(OM) 2 ), CH 2 =CH((CF 2 ) 4 P(O)(OM) 2 ), CH 2 =CH((CF 2 ) 3 P(O)(OM) 2 ), etc., where M is the same as above.

[0816] The compound represented by the general formula (4) is preferably at least one selected from the group consisting of the following compounds, wherein the compound is represented by the general formula (5):

[0817] CX 2 =CY(-CZ 2 -O-Rf-Y 3 ) (5)

[0818] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Z is the same or different and 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 having an ether bond. Y 3 Same as above) and the compound represented by the general formula (6):

[0819] CX 2 =CY(-O-Rf-Y 3 ) (6)

[0820] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. 3 Same as above);And general formula (7):

[0821] CX 2 =CY(-Rf-Y 3 ) (7)

[0822] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. 3 Same as above).

[0823] The fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond is an alkylene group having no structure with an oxygen atom at the end and having an ether bond between carbon atoms.

[0824] In the general formula (5), X is -H or -F. Both Xs may be -F, or at least one of them may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0825] In the general formula (5), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group.

[0826] The alkyl group is an alkyl group not containing fluorine atoms and may have at least 1 carbon atom. The alkyl group may have preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms.

[0827] The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0828] As the above-mentioned Y, -H, -F or -CF is preferred. 3 , more preferably -F.

[0829] In the general formula (5), Z is the same or different and is -H, -F, alkyl or fluoroalkyl.

[0830] The alkyl group is an alkyl group not containing fluorine atoms and may have at least 1 carbon atom. The alkyl group may have preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms.

[0831] The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0832] As the above Z, -H, -F or -CF is preferred. 3 , more preferably -F.

[0833] In the general formula (5), at least one of X, Y and Z preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0834] In the general formula (5), 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.

[0835] The number of carbon atoms in the fluorinated alkylene group is preferably 2 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less. Examples of the fluorinated alkylene group include -CF 2 -、-CH 2 CF 2 -、-CF 2 CF 2 -、-CF 2 CH 2 -、-CF 2 CF 2 CH 2 -、-CF(CF 3 )-、-CF(CF 3 )CF 2 -、-CF(CF 3 )CH 2 - etc. The above-mentioned fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0836] The number of carbon atoms in the fluorinated alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms in the fluorinated alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less.

[0837] As the fluorine-containing alkylene group having an ether bond, for example, the following formula is also preferred:

[0838] [Chemistry 27]

[0839]

[0840] (Where Z 1 F or CF 3 ; Z 2 and Z 3 H or F; Z 4 H, F or CF 3; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0841] Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF 3 )CF 2 -O-CF(CF 3 )-、-(CF(CF 3 )CF 2 -O) n -CF(CF 3 )-(wherein n is an integer from 1 to 10), -CF(CF 3 )CF 2 -O-CF(CF 3 )CH 2 -、-(CF(CF 3 )CF 2 -O) n -CF(CF 3 )CH 2 -(wherein n is an integer from 1 to 10), -CH 2 CF 2 CF 2 O-CH 2 CF 2 CH 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 -、-CF 2 CF 2 CF 2 O-CF 2 CF 2 CH 2 -、-CF 2 CF 2 O-CF 2 -、-CF 2 CF 2 O-CF 2 CH 2 - etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0842] In the general formula (5), Y 3 Preferred are -COOM, -SO 3 M or -OSO 3 M (M is H, metal atom, NR 7y 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R7y is H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring).

[0843] As R 7y The organic group in is preferably an alkyl group.

[0844] As R 7y , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 of alkyl.

[0845] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred.

[0846] As M, -H, a metal atom or NR 7 4 , more preferably -H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4 , further preferably -H, -Na, -K, -Li or NH 4 , and more preferably -H, -Na, -K or NH 4 , particularly preferably -H, -Na or NH 4 , most preferably -H or -NH 4 .

[0847] As the above Y 3 , preferably -COOM or -SO 3 M is more preferably -COOM.

[0848] The compound represented by the general formula (5) is preferably a compound (5a) represented by the general formula (5a).

[0849] CH 2 =CF(-CF 2 -O-Rf-Y 3 )(5a)

[0850] (In the formula, Rf and Y 3 Same as above.)

[0851] Specific examples of the compound represented by the general formula (5a) include the following:

[0852] [Chemistry 28]

[0853]

[0854] (Where Z 1 F or CF 3 ; Z 2 and Z3 H or F; Z 4 H, F or CF 3 ; p1+q1+r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, Y 3 Same as above. Where Z 3 and Z 4 When all are H, p1+q1+r1+s1 is not 0). More specifically, preferably,

[0855] [Chemistry 29]

[0856]

[0857] CH 2 =CFCF 2 OCH 2 CF 2 -Y 3 , CH 2 =CFCF 2 O(CH 2 CFCF 2 O)CH 2 CF 2 -Y 3 ,

[0858] CH 2 =CFCF 2 OCH 2 CF 2 CH 2 -Y 3 ,

[0859] CH 2 =CFCF 2 O(CH 2 CF 2 CF 2 O)CH 2 CF 2 CH 2 -Y 3 ,

[0860] CH 2 =CFCF 2 OCF 2 CF 2 -Y 3 , CH 2 =CFCF 2 O(CF 2 CF 2 CF 2 O)CF 2 CF 2 -Y 3 ,

[0861] CH 2 =CFCF 2 OCF 2 CF 2 CH 2 -Y 3 ,

[0862] CH 2 =CFCF 2 O(CF 2 CF 2 CF 2 O)CF 2 CF 2 CH 2 -Y 3 ,

[0863] CH 2 =CFCF 2 OCF 2 -Y 3 , CH 2 =CFCF 2 O(CF 2 CF 2 O)CF 2 -Y 3 ,

[0864] CH 2 =CFCF 2 OCF 2 CH 2 -Y 3 ,

[0865] CH 2 =CFCF 2 O(CF 2 CF 2 O)CF 2 CH 2 -Y 3 ,

[0866] etc., among which preferably

[0867] [Chemistry 30]

[0868]

[0869] As the compound represented by the general formula (5a), Y in the formula (5a) is preferably 3 is -COOM, particularly preferably selected from CH 2 =CFCF 2 OCF(CF 3 )COOM and CH 2 =CFCF 2 OCF(CF3 )CF 2 OCF(CF 3 )COOM (wherein M is the same as defined above), more preferably CH 2 =CFCF 2 OCF(CF 3 )COOM.

[0870] The compound represented by the general formula (5) is preferably a compound (5b) represented by the general formula (5b).

[0871] CX 2 2 =CFCF 2 -O-(CF(CF 3 )CF 2 O) n5 -CF(CF 3 )-Y 3 (5b)

[0872] (In the formula, each X 2 The same, represents F or H. n5 represents 0 or an integer from 1 to 10, Y 3 Same as the above definition.)

[0873] In the above formula (5b), from the perspective of stability of the obtained aqueous dispersion, the above n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1. From the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 -COOM is preferred. M is preferably H or NH from the viewpoint that it is less likely to remain as an impurity and the heat resistance of the obtained molded product is improved. 4 .

[0874] Examples of the compound represented by the above formula (5b) include CH 2 =CFCF 2 OCF(CF 3 )COOM、CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )COOM (wherein M has the same definition as above).

[0875] In addition, examples of the compound represented by the general formula (5) include compounds represented by the general formula (5c) and the like.

[0876] CF 2 =CFCF 2 -O-Rf-Y 3 (5c)

[0877] (In the formula, Rf and Y 3 Same as above.)

[0878] More specifically, we can cite

[0879] [Chemistry 31]

[0880] CF 2 =CFCF 2 OCF 2 CF 2 CF 2 -Y 3 ,

[0881]

[0882] CF 2 =CFCF 2 OCF 2 CF 2 CF 2 CH 2 -Y 3 ,

[0883] wait.

[0884] In the general formula (6), X is -H or -F. Both Xs may be -F, or at least one of them may be -H. For example, one may be -F and the other may be -H, or both may be -H.

[0885] In the general formula (6), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group.

[0886] The alkyl group is an alkyl group not containing fluorine atoms and may have at least 1 carbon atom. The alkyl group may have preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms.

[0887] The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0888] As the above-mentioned Y, -H, -F or -CF is preferred. 3 , more preferably -F.

[0889] In the general formula (6), at least one of X and Y preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0890] In the general formula (6), 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.

[0891] The number of carbon atoms in the fluorinated alkylene group is preferably 2 or more. In addition, the number of carbon atoms in the fluorinated alkylene group is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less. Examples of the fluorinated alkylene group include -CF 2 -、-CH 2 CF 2 -、-CF 2 CF 2 -、-CF 2 CH 2 -、-CF 2 CF 2 CH 2 -、-CF(CF 3 )-、-CF(CF 3 )CF 2 -、-CF(CF 3 )CH 2 - etc. The above-mentioned fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0892] In the above general formula (6), Y 3 Preferred are -COOM, -SO 3 M or -OSO 3 M (M is H, metal atom, NR 7y 4 , an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7y is H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring).

[0893] As R 7y As R 7y , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 of alkyl.

[0894] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred.

[0895] As M, -H, a metal atom or NR 7 4 , more preferably -H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4 , further preferably -H, -Na, -K, -Li or NH 4 , and more preferably -H, -Na, -K or NH 4 , particularly preferably -H, -Na or NH4 , most preferably -H or -NH 4 .

[0896] As the above Y 3 , preferably -COOM or -SO 3 M is more preferably -COOM.

[0897] The compound represented by the general formula (6) is preferably at least one selected from the group consisting of compounds represented by the general formulae (6a), (6b), (6c), (6d) and (6e).

[0898] CF 2 =CF-O-(CF 2 ) n1 -Y 3 (6a)

[0899] (where n1 represents an integer from 1 to 10, Y 3 Same as the above definition.)

[0900] CF 2 =CF-O-(CF 2 C(CF 3 )F) n2 -Y 3 (6b)

[0901] (where n2 represents an integer from 1 to 5, Y 3 Same as the above definition.)

[0902] CF 2 =CF-O-(CFX 1 ) n3 -Y 3 (6c)

[0903] (Where X 1 Indicates F or CF 3 , n3 represents an integer from 1 to 10, Y 3 Same as the above definition.)

[0904] CF 2 =CF-O-(CF 2 CFX 1 O) n4 -(CF 2 ) n6 -Y 3 (6d)

[0905] (wherein, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and Y 3 and X 1 Same as the above definition.)

[0906] CF2 =CF-O-(CF 2 CF 2 CFX 1 O) n5 -CF 2 CF 2 CF 2 -Y 3 (6e)

[0907] (where n5 represents an integer from 0 to 10, Y 3 and X 1 Same as the above definition.)

[0908] In the above formula (6a), the above n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. From the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 -COOM is preferred. M is preferably H or NH from the viewpoint that it is less likely to remain as an impurity and the heat resistance of the obtained molded article is improved. 4 .

[0909] Examples of the compound represented by the above formula (6a) include CF 2 =CF-O-CF 2 COOM, CF 2 =CF(OCF 2 CF 2 COOM), CF 2 =CF(OCF 2 CF 2 CF 2 COOM) (wherein, M has the same meaning as above).

[0910] In the above formula (6b), from the perspective of the stability of the obtained aqueous dispersion, the above n2 is preferably an integer of 3 or less, and from the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, Y 3 -COOM is preferred. M is preferably H or NH from the viewpoint that it is less likely to remain as an impurity and the heat resistance of the obtained molded article is improved. 4 .

[0911] In the above formula (6c), from the viewpoint of water solubility, the above n3 is preferably an integer of 5 or less, and from the viewpoint of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 It is preferably -COOM. From the perspective of improving dispersion stability, the above M is preferably H or NH 4 .

[0912] In the above formula (6d), from the perspective of the stability of the aqueous dispersion, the above X 1Preferably -CF 3 From the perspective of water solubility, the above n4 is preferably an integer of 5 or less, and from the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 Preferably -COOM, the above M is preferably H or NH 4 .

[0913] Examples of the compound represented by the above formula (6d) include CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 COOM, CF 2 =CFOCF 2 CF(CF 3 )OCF 2 COOM, CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CF 2 COOM (where M represents H, NH 4 or alkali metals).

[0914] In the general formula (6e), from the viewpoint of water solubility, the above n5 is preferably an integer of 5 or less, and from the viewpoint of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 Preferably -COOM, the above M is preferably H or NH 4 .

[0915] Examples of the compound represented by the general formula (6e) include CF 2 =CFOCF 2 CF 2 CF 2 COOM (where M represents H, NH 4 or alkali metals).

[0916] In the general formula (7), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In the general formula (7), at least one of X and Y preferably contains a fluorine atom.

[0917] The compound represented by the general formula (7) is preferably selected from the general formula (7a):

[0918] CF 2 =CF-(CF 2 ) n1 -Y 3 (7a)

[0919] (where n1 represents an integer from 1 to 10, Y 3 The compounds represented by the general formula (7b) are the same as those defined above:

[0920] CF 2 =CF-(CF 2 C(CF 3 )F) n2 -Y 3 (7b)

[0921] (where n2 represents an integer from 1 to 5, Y 3 At least one of the compounds represented by the group consisting of the compounds shown in the above definition).

[0922] The above Y 3 Preferred-SO 3 M or -COOM, M is preferably H, metal atom, NR 7y 4 , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 7y represents H or an organic group.

[0923] In the above formula (7a), the above n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. From the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 -COOM is preferred. M is preferably H or NH from the viewpoint that it is less likely to remain as an impurity and the heat resistance of the obtained molded article is improved. 4 .

[0924] Examples of the compound represented by the above formula (7a) include CF 2 =CFCF 2 COOM (wherein M has the same definition as above).

[0925] In the above formula (7b), from the perspective of the stability of the obtained aqueous dispersion, the above n2 is preferably an integer of 3 or less, and from the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, Y 3 -COOM is preferred. M is preferably H or NH from the viewpoint that it is less likely to remain as an impurity and the heat resistance of the obtained molded article is improved. 4 .

[0926] The above-mentioned modified monomer preferably includes a modified monomer (A), preferably includes at least one selected from the group consisting of compounds represented by general formula (5a), general formula (5c), general formula (6a), general formula (6b), general formula (6c) and general formula (6d), and more preferably includes a compound represented by general formula (5a) or general formula (5c).

[0927] When using modified monomer (A) as modified monomer, the content of modified monomer (A) unit is preferably in the range of 0.00001 mass % to 1.0 mass % relative to the total polymerized units of the above-mentioned TFE polymer (PTFE). As the lower limit, it is more preferably 0.0001 mass %, more preferably 0.0005 mass %, further preferably 0.001 mass %, and further more preferably 0.005 mass %. As the upper limit, it is 0.90 mass %, 0.50 mass %, 0.40 mass %, 0.30 mass %, 0.20 mass %, 0.15 mass %, 0.10 mass %, 0.08 mass %, 0.05 mass %, 0.01 mass %.

[0928] In the manufacture of the above-mentioned TFE polymer, polymer (I) can be used within the scope of use in the above-mentioned manufacturing method of the present invention. The concentration of polymer (I) is not particularly limited as long as it is within the above-mentioned range. If the amount added is too much, needle-shaped particles with a large aspect ratio are generated, and the aqueous dispersion is gel-like and the stability is likely to be impaired. The lower limit of the amount of polymer (I) is preferably 0.0001% by mass, more preferably 0.001% by mass, further preferably 0.01% by mass, and particularly preferably 0.02% by mass relative to the aqueous medium. The upper limit of the amount of the above-mentioned polymer (I) is preferably 10% by mass, more preferably 5% by mass relative to the aqueous medium.

[0929] The polymer (I) may be added to the reaction vessel all at once before the start of polymerization, may be added all at once after the start of polymerization, may be added in several portions during polymerization, or may be added continuously during polymerization.

[0930] In the manufacture of the above-mentioned TFE polymer, as a polymerization initiator, organic peroxides such as persulfate (for example ammonium persulfate), disuccinic acid peroxide, diglutaric acid peroxide, etc. can be used alone or in the form of a mixture thereof. In addition, it is also possible to share with reducing agents such as sodium sulfite to make a redox system for use. Furthermore, free radical scavengers such as hydroquinone and catechol can also be added during polymerization, or a decomposing agent of peroxides such as ammonium sulfite can be added to adjust the free radical concentration in the system.

[0931] As the polymerization initiator of the above-mentioned redox system, it is preferred to use a redox initiator in which an oxidant and a reductant are combined. As the oxidant, persulfate, organic peroxide, potassium permanganate, manganese triacetate, ammonium cerium nitrate, etc. can be mentioned. As the reductant, sulfite, bisulfite, bromate, diimide, oxalic acid, etc. can be mentioned. As persulfate, ammonium persulfate and potassium persulfate can be mentioned. As sulfite, sodium sulfite and ammonium sulfite can be mentioned. In order to increase the decomposition rate of the initiator, it is also preferred to add copper salts and iron salts to the combination of redox initiators. As copper salts, copper sulfate (II) can be mentioned, and as iron salts, iron sulfate (II) can be mentioned.

[0932] As the above-mentioned redox initiator, for example, potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / ferric sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / bisulfite, etc. can be mentioned, preferably potassium permanganate / oxalic acid. In the case of using a redox initiator, either the oxidant or the reductant can be put into a polymerization kettle in advance, and then the other can be added continuously or intermittently to initiate polymerization. For example, in the case of using potassium permanganate / oxalic acid, it is preferred to put oxalic acid into the polymerization kettle and continuously add potassium permanganate thereto.

[0933] In the production of the above-mentioned TFE polymer, known substances can be used as chain transfer agents, for example, saturated hydrocarbons such as methane, ethane, propane, butane, halogenated hydrocarbons such as methyl chloride, dichloromethane, difluoroethane, alcohols such as methanol, ethanol, isopropanol, hydrogen, etc., preferably substances in a gaseous state at normal temperature and pressure.

[0934] The amount of the chain transfer agent used is usually 1 to 10,000 ppm by mass, preferably 1 to 5,000 ppm by mass, based on the total amount of TFE supplied.

[0935] In the production of the above-mentioned TFE polymer, 2 to 10 parts by mass of a saturated hydrocarbon having 12 or more carbon atoms which is substantially inert in the reaction and is liquid under the above-mentioned reaction conditions may be further used as a dispersion stabilizer for the reaction system with respect to 100 parts by mass of the aqueous medium. In addition, ammonium carbonate, ammonium phosphate, etc. may be added as a buffer for adjusting the pH during the reaction.

[0936] When the polymerization of TFE is terminated, an aqueous dispersion having a solid content concentration of 1.0% to 70% by mass and an average primary particle size of 50 nm to 500 nm can be obtained.

[0937] The lower limit of the solid content concentration is preferably 5% by mass, more preferably 8% by mass. The upper limit is not particularly limited, and may be 40% by mass or 35% by mass.

[0938] The lower limit of the average primary particle size is preferably 100 nm, more preferably 150 nm, and the upper limit is preferably 400 nm, more preferably 350 nm.

[0939] The above average primary particle size can be measured by dynamic light scattering. Regarding the above average primary particle size, an aqueous dispersion having a solid content concentration adjusted to about 1.0% by mass can be prepared, and the dynamic light scattering method can be used to measure the solution at 25°C, a solvent (water) having a refractive index of 1.3328, a solvent (water) having a viscosity of 0.8878 mPa·s, and a cumulative 70 times. As a dynamic light scattering method, for example, ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) can be used.

[0940] Fine powder can be produced by precipitating the above-mentioned aqueous dispersion. The aqueous dispersion of the above-mentioned TFE polymer can be used for various purposes in the form of fine powder after precipitation, washing and drying. In the case of precipitating the aqueous dispersion of the above-mentioned TFE polymer, usually, the aqueous dispersion obtained by polymerization of the polymer emulsion is diluted with water to a polymer concentration of 5% to 20% by mass. According to the situation, after adjusting the pH to neutral or alkaline, it is stirred more vigorously in a container with a stirrer than the stirring in the reaction. In the above-mentioned precipitation, water-soluble organic compounds such as methanol and acetone, inorganic salts such as potassium nitrate and ammonium carbonate, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. can be added as precipitants and stirred at the same time. The above-mentioned precipitation can also be carried out continuously using a pipeline mixer, etc.

[0941] From the viewpoint of productivity, the concentration of the uncoagulated TFE polymer in the wastewater generated by the coagulation is preferably low, more preferably less than 0.4% by mass, and particularly preferably less than 0.3% by mass.

[0942] By adding pigments for coloring or various fillers for improving mechanical properties before or during the above precipitation, a pigment-containing or filler-containing TFE polymer fine powder uniformly mixed with the pigment or filler can be obtained.

[0943] The drying of the wet powder obtained by precipitating the aqueous dispersion of the TFE polymer is usually carried out by using vacuum, high frequency, hot air and other means while keeping the wet powder in a state where it is almost immobile, preferably in a static state. Friction between powders, especially at high temperatures, usually has an adverse effect on fine powder TFE polymers. This is because the particles composed of the TFE polymer have the property of simply fibrillating even when subjected to a small shear force, thereby losing the originally stable particle structure.

[0944] The drying is performed at a drying temperature of 10°C to 300°C, preferably 100°C to 300°C.

[0945] The obtained TFE polymer fine powder is preferably used for molding. Suitable uses include pipes for oil pressure systems and fuel systems of aircraft and automobiles, flexible hoses for reagents and steam, and wire coatings.

[0946] In addition, the aqueous dispersion of the TFE polymer obtained by the above polymerization is preferably stabilized by adding a nonionic surfactant, further concentrated, and an organic or inorganic filler is added according to the purpose to prepare a composition for various uses. The above composition can be coated on a substrate formed of metal or ceramic to form a coating surface having non-stickiness and low friction coefficient, gloss, smoothness, wear resistance, weather resistance and heat resistance, and is suitable for coating of rollers or cooking devices, impregnation processing of glass cloth, etc.

[0947] The organosol of TFE polymer can also be prepared by the above-mentioned aqueous dispersion. The above-mentioned organosol can comprise the above-mentioned TFE polymer and an organic solvent. As the above-mentioned organic solvent, ether solvents, ketone solvents, alcohol solvents, amide solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents can be enumerated, and N-methyl-2-pyrrolidone, dimethylacetamide etc. can be used appropriately. The preparation of the above-mentioned organosol can be implemented by the method described in International Publication No. 2012 / 002038.

[0948] The aqueous dispersion of the TFE polymer or the fine powder of the TFE polymer is also preferably used as a processing aid. When used as a processing aid, the melt strength of the main polymer during melt processing can be improved by mixing the aqueous dispersion or the fine powder with the main polymer, etc., and the mechanical strength, electrical properties, flame retardancy, anti-drip properties during combustion, and slip properties of the obtained polymer can be improved.

[0949] The aqueous dispersion of the TFE polymer or the fine powder of the TFE polymer is also preferably used as a binder for batteries or for dust prevention.

[0950] The aqueous dispersion of the TFE polymer or the fine powder of the TFE polymer is preferably used as a processing aid after being compounded with a resin other than the TFE polymer. The aqueous dispersion or the fine powder is suitable as a raw material for PTFE described in, for example, Japanese Patent Publication No. 11-49912, U.S. Patent No. 5804654, Japanese Patent Publication No. 11-29679, and Japanese Patent Publication No. 2003-2980. The processing aid using the aqueous dispersion or the fine powder is not inferior to the processing aids described in the above publications.

[0951] The aqueous dispersion of the TFE polymer is preferably mixed with an aqueous dispersion of a melt-processable fluororesin and precipitated to form a co-precipitated powder. The co-precipitated powder is suitable as a processing aid.

[0952] Examples of the melt-processable fluororesin include FEP, PFA, TFE / perfluoroallyl ether copolymer, ETFE, and ethylene / TFE / HFP copolymer [EFEP]. Among them, FEP is preferred.

[0953] The aqueous dispersion also preferably contains the melt-processable fluororesin. Examples of the melt-processable fluororesin include FEP, PFA, TFE / perfluoroallyl ether copolymer, ETFE, EFEP, and the like. The aqueous dispersion containing the melt-processable fluororesin can be used as a coating. The melt-processable fluororesin can fully fuse the particles of the TFE polymer to each other, thereby improving film-forming properties and making the resulting coating glossy.

[0954] The non-fluorine-containing resin to which the coprecipitated powder is added may be in powder, granular or emulsion form. From the perspective of fully mixing the resins, the addition is preferably performed while applying shear force using a known method such as extrusion kneading or roll kneading.

[0955] The aqueous dispersion of the TFE polymer is also preferably used as a dust suppressing agent. The dust suppressing agent can be used in the following method: a method of mixing with a dust-generating substance and applying compression-shearing action to the mixture at a temperature of 20°C to 200°C to thereby fibrillate the TFE polymer and suppress dust of the dust-generating substance; for example, the method described in Japanese Patent No. 2827152, Japanese Patent No. 2538783, etc.

[0956] The aqueous dispersion of the TFE polymer can be suitably used in the dust suppression treatment agent composition described in, for example, International Publication No. 2007 / 004250, and can also be suitably used in the dust suppression treatment method described in International Publication No. 2007 / 000812.

[0957] The dust suppression agent is suitable for use in dust suppression in the fields of building materials, soil stabilization materials, solidification materials, fertilizers, filling treatment of incineration ash and harmful substances, explosion-proofing, cosmetics, and litter for pet excretion represented by cat litter.

[0958] The aqueous dispersion of the TFE polymer is also preferably used as a raw material for obtaining TFE polymer fibers by a dispersion spinning method. The dispersion spinning method refers to a method in which the aqueous dispersion of the TFE polymer is mixed with an aqueous dispersion of a matrix polymer, the mixture is extruded to form an intermediate fiber structure, and the intermediate fiber structure is calcined to decompose the matrix polymer and sinter the TFE polymer particles to obtain TFE polymer fibers.

[0959] The high molecular weight PTFE powder obtained by polymerization has stretchability and non-melt processability, and is also useful as a raw material for a stretched body (porous body).

[0960] When the stretched body is a membrane (PTFE stretched membrane or PTFE porous membrane), it can be stretched by a known PTFE stretching method. By stretching, high molecular weight PTFE is easily fibrillated to form a PTFE porous body (membrane) composed of nodes and fibers.

[0961] Preferably, a sheet-shaped or rod-shaped paste extrudate is roll-stretched in the extrusion direction to obtain a uniaxially stretched film.

[0962] Furthermore, by stretching in the width direction using a tenter or the like, a biaxially stretched film can also be obtained.

[0963] It is also preferred to perform a semi-firing treatment before stretching.

[0964] This stretched PTFE body is a porous body having a high porosity, and can be suitably used as a filter material for various microfiltration filters such as air filters and reagent filters, a support material for polymer electrolyte membranes, and the like.

[0965] Furthermore, it is also useful as a material for products used in the fields of fibers, medicine, electrochemistry, sealing materials, air filtration, ventilation / internal pressure regulation, liquid filtration, and general consumables.

[0966] Specific uses are exemplified below.

[0967] Electrochemical field

[0968] Dielectric material prepreg, EMI shielding material, heat transfer material, etc. More specifically, printed circuit board, electromagnetic shielding material, insulating heat transfer material, insulating material, etc.

[0969] Sealing material field

[0970] Gaskets, sealing pads, pump diaphragms, pump tubes, sealing materials for aircraft, etc.

[0971] Air filtration field

[0972] ULPA filter (for semiconductor manufacturing), HEPA filter (for hospital and semiconductor manufacturing), cylindrical cartridge filter (for industrial use), bag filter (for industrial use), heat-resistant bag filter (for exhaust gas treatment), heat-resistant pleated filter (for exhaust gas treatment), SINBRAN filter (for industrial use), catalytic filter (for exhaust gas treatment), filter with adsorbent (for HDD assembly), ventilation filter with adsorbent (for HDD assembly), ventilation filter (for HDD assembly, etc.), filter for vacuum cleaner (for vacuum cleaner), general-purpose multilayer felt, cartridge filter for GT (for GT interchangeable parts), cooling filter (for electronic equipment housing), etc.

[0973] Ventilation / internal pressure adjustment area

[0974] Freeze-drying materials such as freeze-drying containers, automotive ventilation materials suitable for electronic circuits or lamps, container uses such as container covers, protective ventilation uses for electronic devices including small terminals such as tablet terminals and mobile phone terminals, medical ventilation uses, etc.

[0975] Liquid filtration field

[0976] Semiconductor liquid filters (for semiconductor manufacturing), hydrophilic PTFE filters (for semiconductor manufacturing), filters suitable for chemicals (for reagent processing), filters for pure water production lines (for pure water production), backwash type liquid filtration filters (for industrial wastewater treatment), etc.

[0977] General consumables field

[0978] Clothing, cable guide tubes (removable wires suitable for motorcycles), motorcycle clothing, cast pads (medical protective gear), vacuum cleaner filters, bagpipes (musical instruments), cables (signal cables for guitars, etc.), strings (for stringed instruments), etc.

[0979] Fiber field

[0980] PTFE fiber (fibrous material), sewing thread (fabric), knitting thread (fabric), rope, etc.

[0981] Medical field

[0982] Embedded products (stretchable products), artificial blood vessels, catheters, general surgery (tissue reinforcement materials), head and neck products (dura mater substitutes), oral health (tissue regeneration medicine), plastic surgery (bandages), etc.

[0983] The production method of the present invention can also produce low-molecular-weight PTFE.

[0984] Low molecular weight PTFE can be produced by polymerization, or by reducing the molecular weight of high molecular weight PTFE obtained by polymerization by a known method (thermal decomposition, radiation irradiation decomposition, etc.).

[0985] Low molecular weight PTFE (also called PTFE powder) with a molecular weight of less than 600,000 has excellent chemical stability, extremely low surface energy, and is not prone to fibrillation. Therefore, it is suitable for the manufacture of plastics, inks, cosmetics, coatings, greases, office automation equipment parts, toners, etc. as an additive for the purpose of improving slippage and the texture of the coating surface (for example, see Japanese Patent Publication No. 10-147617).

[0986] In addition, the polymerization initiator and polymer (I) may be further dispersed in an aqueous medium in the presence of a chain transfer agent, and TFE or a monomer copolymerizable with TFE and TFE may be polymerized to obtain low molecular weight PTFE. In this case, the chain transfer agent is preferably at least one selected from the group consisting of alkanes having 2 to 4 carbon atoms. Specifically, methane, ethane, propane, butane, isobutane are more preferred, and ethane and propane are further preferred. In this case, the amount of the chain transfer agent is preferably 10 mass ppm or more or more than 10 mass ppm relative to the aqueous medium.

[0987] When the low molecular weight PTFE obtained by the above polymerization is used as a powder, it can be made into powder particles by precipitating the above aqueous dispersion.

[0988] In the present invention, high molecular weight PTFE refers to PTFE that is not melt-processable and fibrillating, while low molecular weight PTFE refers to PTFE that is melt-processable and not fibrillating.

[0989] The non-melt processability mentioned above refers to a property in which the melt flow rate cannot be measured at a temperature higher than the crystallization melting point according to ASTM D 1238 and D 2116.

[0990] The presence or absence of fibrillation can be judged by "paste extrusion", which is a representative method for molding a powder made from a polymer of TFE, i.e., "high molecular weight PTFE powder". This is because, usually, when paste extrusion can be performed, high molecular weight PTFE has fibrillation. In the case where the unfired molded product obtained by paste extrusion does not have substantial strength or elongation, for example, in the case where the elongation is 0% and it breaks if stretched, it can be considered as not having fibrillation.

[0991] The standard specific gravity (SSG) of the high molecular weight PTFE is preferably 2.130 to 2.280. The standard specific gravity is measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895-89. In the present invention, "high molecular weight" means that the standard specific gravity is within the above range.

[0992] The complex viscosity (melt viscosity) of the low molecular weight PTFE at 340°C is 1×10 2 Pa·s~7×10 5 Pa·s. In the present invention, "low molecular weight" means that the above complex viscosity is within the above range. Melt viscosity is the following value: according to ASTM D1238, using a flow tester (manufactured by Shimadzu Corporation) and A 2 g sample preliminarily heated at 380° C. for 5 minutes was maintained at the above temperature under a load of 0.7 MPa in a mold, and the obtained value was the above melt viscosity.

[0993] The complex viscosity (melt viscosity) of above-mentioned high molecular weight PTFE is significantly higher than above-mentioned low molecular weight PTFE, and is difficult to measure its accurate complex viscosity.On the other hand, the complex viscosity of above-mentioned low molecular weight PTFE can be measured, but it is difficult to obtain the molded product that can be used for the mensuration of standard specific gravity by above-mentioned low molecular weight PTFE, and is difficult to measure its accurate standard specific gravity.Therefore, among the present invention, standard specific gravity is adopted as the index of the molecular weight of above-mentioned high molecular weight PTFE, and complex viscosity is adopted as the index of the molecular weight of above-mentioned low molecular weight PTFE.It should be noted that, for above-mentioned high molecular weight PTFE and above-mentioned low molecular weight PTFE, the assay method that can directly determine the specific molecular weight is all unknown.

[0994] The peak temperature of the high molecular weight PTFE is preferably 333° C. to 347° C., more preferably 335° C. to 345° C. The peak temperature of the low molecular weight PTFE is preferably 322° C. to 333° C., more preferably 324° C. to 332° C. The peak temperature can be determined by heating PTFE that has not been heated to a temperature of 300° C. or higher at 10° C. / min using TG / DTA (differential thermal and thermogravimetric simultaneous measurement apparatus) to a temperature corresponding to a local maximum value that appears in the resulting differential thermal (DTA) curve.

[0995] The peak temperature of PTFE may be 322°C to 347°C.

[0996] When the PTFE is high molecular weight PTFE, the upper limit of the peak temperature of the PTFE may be 347°C or lower, 346°C or lower, 345°C or lower, 344°C or lower, 343°C or lower, 342°C or lower, 341°C or lower, or 340°C or lower.

[0997] When the PTFE is high molecular weight PTFE, the lower limit of the peak temperature of the PTFE may be 333° C. or higher, or 335° C. or higher.

[0998] When the PTFE is low molecular weight PTFE, the upper limit of the peak temperature of the PTFE may be 333° C. or lower, or 332° C. or lower.

[0999] When the PTFE is low molecular weight PTFE, the lower limit of the peak temperature of the PTFE may be 322° C. or higher, or 324° C. or higher.

[1000] The average primary particle size of the primary particles of low molecular weight PTFE is preferably 10 nm to 200 nm, more preferably 20 nm or more, more preferably 140 nm or less, further preferably 150 nm or less, and particularly preferably 90 nm or less. A relatively small average primary particle size of the primary particles can be obtained, for example, by adding a modifying monomer to the polymerization system at the initial stage of TFE polymerization.

[1001] The average primary particle size of the primary particles of low molecular weight PTFE can be measured by dynamic light scattering. First, make a low molecular weight PTFE aqueous dispersion adjusted to about 1.0 mass % by polymer solid content concentration, use dynamic light scattering, set the measurement temperature to be 25 ° C, the refractive index of the solvent (water) to be 1.3328, the viscosity of the solvent (water) to be 0.8878mPa·s, and the cumulative number of times to be 70, thus can be measured. In the dynamic light scattering method, for example, ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) can be used.

[1002] In the heat of fusion curve of PTFE that has not been heated to a temperature of 300°C or higher and is heated at a rate of 10°C / min using a differential scanning calorimeter [DSC], the high molecular weight PTFE preferably has at least one endothermic peak in the range of 333°C to 347°C, and the heat of fusion at 290°C to 350°C calculated from the heat of fusion curve is 62 mJ / mg or more.

[1003] An unfired tape (green tape) can also be obtained from the PTFE fine powder obtained above.

[1004] (II) Melt-processable fluororesin

[1005] (1) In the production method of the present invention, the polymerization of FEP is preferably performed at a polymerization temperature of 10° C. to 150° C. and a polymerization pressure of 0.3 MPaG to 6.0 MPaG.

[1006] The preferred monomer composition (mass %) of FEP is TFE:HFP=(60-95):(5-40), and more preferably (85-92):(8-15). The above FEP may be further modified by using perfluoro(alkyl vinyl ether) as the third component in an amount of 0.1% to 2% by mass of the total monomers.

[1007] In the polymerization of FEP, the polymer (I) can be used within the range of use in the production method of the present invention, and is usually added in an amount of 0.0001% by mass to 10% by mass based on 100% by mass of the aqueous medium.

[1008] In the polymerization of FEP, cyclohexane, methanol, ethanol, propanol, ethane, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, dichloromethane, methyl chloride, etc. are preferably used as the chain transfer agent, and ammonium carbonate, disodium hydrogen phosphate, etc. are preferably used as the pH buffer.

[1009] The aqueous dispersion of FEP obtained in the manufacturing method of the present invention can be subjected to post-treatment such as concentration as needed, dried, and made into powder, and then melt-extruded to form pellets. The aqueous medium in the aqueous dispersion of FEP can contain additives such as nonionic surfactants as needed, and can also contain water-soluble organic solvents such as water-soluble alcohols, or can contain no water-soluble organic solvents.

[1010] In addition, as long as the extrusion conditions are generally capable of pelletizing, the melt extrusion may be performed by appropriately setting the extrusion conditions.

[1011] In the production method of the present invention, the obtained FEP may have -CF at least one of the polymer main chain and the polymer side chain. 3 , -CF 2 H, etc., preferably -COOH, -CH 2 OH, -COF, -CF=CF-, -CONH 2 、-COOCH 3 The content of thermally unstable groups (hereinafter referred to as "unstable terminal groups") is low or absent.

[1012] The unstable terminal group is chemically unstable, and thus not only reduces the heat resistance of the resin but also causes an increase in the attenuation of the resulting electric wire.

[1013] In the production method of the present invention, it is preferred that the polymer at the time of polymerization termination is 1×10 6 Unstable terminal groups and -CF 2 The total number of H terminal groups is 50 or less. 6The number of carbon atoms is preferably less than 20, and more preferably less than 5. 2 The H-terminal group can also be absent, all -CF 3 Terminal group.

[1014] Unstable terminal groups and -CF 2 The H-terminal group can be converted to -CF by fluorination 3 The fluorination treatment method is not particularly limited, and examples thereof include a method of exposing the polymer to a fluorine free radical source that generates fluorine free radicals under fluorination treatment conditions. Examples of the fluorine free radical source include fluorine gas, CoF 3 , AgF 2 、UF 6 、OF 2 、N 2 F 2 CF 3 OF and halogen fluoride (such as IF 5 , ClF 3 ) and the like. Among them, a method of directly contacting fluorine gas with the FEP obtained by the manufacturing method of the present invention is preferred. From the aspect of reaction control, the above-mentioned contact is preferably carried out using diluted fluorine gas with a fluorine gas concentration of 10% by mass to 50% by mass. The above-mentioned diluted fluorine gas can be obtained by diluting the fluorine gas with an inert gas such as nitrogen and argon. The above-mentioned fluorine gas treatment is carried out, for example, at a temperature of 100°C to 250°C. It should be noted that the treatment temperature is not limited to the above-mentioned range and can be appropriately set according to the situation. The above-mentioned fluorine gas treatment is preferably carried out by continuously or intermittently supplying diluted fluorine gas into the reactor. The fluorination treatment can be for dry powder after polymerization or for pellets after melt extrusion.

[1015] The FEP obtained by the production method of the present invention has good moldability and is less likely to have poor molding. It also has excellent heat resistance, chemical resistance, solvent resistance, insulation, electrical properties, and the like.

[1016] The method for producing the FEP powder is a method for obtaining the powder by drying and powderizing the FEP obtained by the production method of the present invention.

[1017] The powder may be fluorinated. The method for producing the fluorinated powder is a method for producing the fluorinated powder by supplying fluorine gas to the powder obtained by the method for producing the powder to fluorinate the powder.

[1018] The method for producing the FEP pellets is a method for obtaining pellets by pelletizing the FEP obtained by the production method of the present invention.

[1019] The pellets may be fluorinated. The method for producing the fluorinated pellets is a method for producing the fluorinated pellets by supplying fluorine gas to the pellets obtained by the method for producing the pellets to fluorinate the pellets, thereby producing the fluorinated pellets.

[1020] Therefore, the FEP can be used for the production of various molded products such as covering materials for electric wires, foamed electric wires, cables, and conductive wires, tubes, films, sheets, and filaments.

[1021] (2) In the production method of the present invention, the polymerization of TFE / perfluoro(alkyl vinyl ether) copolymers such as PFA and MFA and TFE / perfluoroallyl ether copolymers is usually preferably carried out at a polymerization temperature of 10° C. to 100° C. and a polymerization pressure of 0.3 MPaG to 6.0 MPaG.

[1022] The preferred monomer composition (mol %) of the TFE / perfluoro(alkyl vinyl ether) copolymer is TFE:perfluoro(alkyl vinyl ether)=(90-99.7):(0.3-10), more preferably (97-99):(1-3). As the above-mentioned perfluoro(alkyl vinyl ether), it is preferred to use a monomer composition of the formula: CF 2 =CFORf 4 (Where Rf 4 It is a substance represented by a perfluoroalkyl group having 1 to 6 carbon atoms).

[1023] The preferred monomer composition (mol %) of the TFE / perfluoroallyl ether copolymer is TFE:perfluoroallyl ether=(90-99.7):(0.3-10), more preferably (97-99):(1-3). As the perfluoroallyl ether, preferably used is a monomer of the formula: CF 2 =CFCF 2 O 4 (Where Rf 4 It is a substance represented by a perfluoroalkyl group having 1 to 6 carbon atoms).

[1024] In the polymerization of the TFE / perfluoro(alkyl vinyl ether) copolymer and the TFE / perfluoroallyl ether copolymer, the polymer (I) can be used within the range of use in the production method of the present invention and is usually added in an amount of 0.0001 to 10% by mass based on 100% by mass of the aqueous medium.

[1025] In the polymerization of the above-mentioned TFE / perfluoro(alkyl vinyl ether) copolymer and TFE / perfluoroallyl ether copolymer, cyclohexane, methanol, ethanol, propanol, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, dichloromethane, methyl chloride, methane, ethane, etc. are preferably used as chain transfer agents, and ammonium carbonate, disodium hydrogen phosphate, etc. are preferably used as pH buffers.

[1026] The aqueous dispersion of TFE / perfluoro(alkyl vinyl ether) copolymers and TFE / perfluoroallyl ether copolymers such as PFA and MFA obtained by the production method of the present invention can be concentrated as needed, dried, made into powders, and then melt-extruded to form pellets. The aqueous medium in the aqueous dispersion can contain additives such as nonionic surfactants as needed, and can also contain water-soluble organic solvents such as water-soluble alcohols, or can contain no water-soluble organic solvents.

[1027] In addition, melt extrusion can be carried out by appropriately setting extrusion conditions as long as the extrusion conditions are generally capable of pelletizing.

[1028] The above copolymer is preferably subjected to a fluorine gas treatment for the purpose of improving the heat resistance thereof and further enhancing the effect of suppressing the permeation of chemicals into the molded article.

[1029] The fluorine treatment is carried out by bringing fluorine gas into contact with a reagent permeation inhibitor. However, since the reaction with fluorine is very exothermic, it is appropriate to dilute the fluorine with an inert gas such as nitrogen. The amount of fluorine in the fluorine / inert gas mixture is 1% to 100% by mass, preferably 10% to 25% by mass. The treatment temperature is 150°C to 250°C, preferably 200°C to 250°C, and the fluorine treatment time is 3 hours to 16 hours, preferably 4 hours to 12 hours. The gas pressure of the fluorine treatment is in the range of 1 atmosphere to 10 atmospheres, and atmospheric pressure is preferably used. When using a reactor under atmospheric pressure, the fluorine / inert gas mixture can be continuously passed into the reactor. As a result, the unstable end of the above-mentioned copolymer is converted into -CF 3 The end is heat stable.

[1030] As a molding method of the above copolymer and its composition, similarly to conventional PFA, a molding method such as compression molding, transfer molding, extrusion molding, injection molding, blow molding, etc. can be applied.

[1031] The desired molded products can be obtained by such a molding method. Examples of molded products include sheets, films, gaskets, round rods, square rods, tube blanks, tubes, round grooves, square grooves, tanks, chip carriers, chip boxes, beakers, filter housings, flow meters, pumps, valves, plugs, connectors, nuts, wires, heat-resistant wires, etc.

[1032] Among these, they can be particularly suitably used for various chemical reaction devices requiring reagent impermeability, semiconductor manufacturing devices, and tubes, tube blanks, tanks, connectors, and the like used in acidic or alkaline reagent supply devices and the like.

[1033] Furthermore, a nonionic surfactant can be appropriately added to an aqueous dispersion of a TFE / perfluoro(alkyl vinyl ether) copolymer and a TFE / perfluoroallyl ether copolymer such as PFA and MFA, and polyethersulfone, polyamideimide and / or polyimide and metal powder can be dissolved or dispersed in an organic solvent as needed to obtain a primer composition. It can also be used in a coating method for coating a metal surface with a fluororesin, the method comprising: applying the primer composition to a metal surface, applying a melt-processable fluororesin composition on the primer layer thus formed, and firing the melt-processable fluororesin composition layer together with the primer layer.

[1034] (3) In the production method of the present invention, the polymerization of ETFE is preferably performed at a polymerization temperature of 10° C. to 100° C. and a polymerization pressure of 0.3 MPaG to 2.0 MPaG.

[1035] The preferred monomer composition (mol%) of ETFE is TFE:ethylene=(50-99):(50-1). As the above-mentioned ETFE, a third monomer may be further used to modify it in the range of 0-20 mass % of all monomers. Preferably, TFE:ethylene:third monomer=(63-94):(27-2):(1-10). As the above-mentioned third monomer, perfluorobutylethylene, perfluorohexylethylene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene, 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH 2 =CFCF 2 CF 2 CF 2 H), 2-trifluoromethyl-3,3,3-trifluoropropene ((CF 3 ) 2 C=CH 2 ).

[1036] In the polymerization of ETFE, the polymer (I) can be used within the range of use in the production method of the present invention, and is usually added in an amount of 0.0001% by mass to 10% by mass based on 100% by mass of the aqueous medium.

[1037] In the polymerization of ETFE, cyclohexane, methanol, ethanol, propanol, ethane, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, etc. are preferably used as a chain transfer agent.

[1038] After the post-treatment such as concentrating the aqueous dispersion of ETFE obtained by the manufacture method of the present invention as required, drying and powdering are carried out, followed by melt extrusion, thereby pellets can be made. The aqueous medium in the above-mentioned aqueous dispersion can contain additives such as nonionic surfactants as required, and can also contain water-soluble organic solvents such as water-soluble alcohols, or can not contain water-soluble organic solvents.

[1039] In addition, melt extrusion can be carried out by appropriately setting extrusion conditions as long as the extrusion conditions are generally capable of pelletizing.

[1040] The sheet of above-mentioned ETFE can be made into sheet by extrusion molding. That is, ETFE powder or pellets can be melted, extruded continuously by a die, and cooled to obtain a sheet-like molded product. In ETFE, additives can be added.

[1041] As additives, known substances can be used appropriately. As specific examples, ultraviolet absorbers, light stabilizers, antioxidants, infrared absorbers, flame retardants, flame retardant fillers, organic pigments, inorganic pigments, dyes, etc. can be cited. From the aspect of excellent weather resistance, inorganic additives are preferred.

[1042] The content of the additive in the ETFE sheet is preferably 20% by mass or less, particularly preferably 10% by mass or less, based on the total mass of the ETFE sheet.

[1043] The ETFE sheet is excellent in mechanical strength and appearance and is therefore suitable as a membrane material (roof material, ceiling material, outer wall material, inner wall material, covering material, etc.) for membrane structure buildings (sports facilities, gardening facilities, atriums, etc.).

[1044] In addition, it can be used not only as a membrane material for membrane structure buildings, but also as a material such as: outdoor panels (soundproof walls, wind fences, wave-breaking fences, garage roofs, shopping centers, pedestrian street side walls, roofing materials), glass scattering prevention films, heat-resistant and water-resistant sheets, building materials (tent materials for tent warehouses, sunshade membrane materials, partial roof materials for lighting, window materials instead of glass, fire-proof partition membrane materials, curtains, outer wall reinforcement, waterproof membranes, smoke-proof membranes, flame-retardant transparent partitions, road reinforcement, interior decoration (lighting, wall surfaces, blinds, etc.), exterior decoration (tents, signs, etc.)), lifestyle and leisure products (fishing rods, rackets, golf clubs, screens, etc.), automotive materials (hoods, vibration-damping materials, car bodies, etc.), aircraft materials, ship materials, home appliance exteriors, storage tanks, container inner walls, filters, construction membrane materials, electronic materials (printed substrates, wiring substrates, insulating films, release films, etc.), surface materials for solar cell modules, reflector protection materials for solar power generation, surface materials for solar water heaters, etc.

[1045] (4) The production method of the present invention can also be used to produce an electrolyte polymer precursor. In the production method of the present invention, the polymerization of the electrolyte polymer precursor is preferably carried out at a polymerization temperature of 10°C to 100°C and a polymerization pressure of 0.1 MPaG to 2.0 MPaG. The electrolyte polymer precursor contains a vinyl ether monomer as shown below, which can be converted into an ion exchange polymer by hydrolysis treatment.

[1046] Examples of the vinyl ether monomer used in the electrolyte polymer precursor include:

[1047] General formula (150): CF 2 =CF-O-(CF 2 CFY 151 -O) n -(CFY 152 ) m -A 151

[1048] (Where Y 151 Indicates fluorine atom, chlorine atom, -SO 2 F or perfluoroalkyl. The perfluoroalkyl group may contain ethereal oxygen and -SO 2 F group. n represents an integer of 0 to 3. n Y 151 Can be the same or different. 152 Represents a fluorine atom, a chlorine atom, or -SO 2 F group. m represents an integer of 1 to 5. m Y 152 Can be the same or different. 151 Indicates -SO 2 X 151 、-COZ 151 or-POZ 152 Z 153 .X 151 Indicates F, Cl, Br, I, -OR 151 or -NR 152 R 153 . Z 151 , Z 152 and Z 153 Same or different, indicates -NR 154 R 155 OR 156 . R 151 , R 152 , R 153 , R 154 , R 155 and R 156The same or different, representing H, ammonium, alkali metal, alkyl containing or not containing fluorine atoms, aryl, or sulfonyl group) is a fluorine-containing monomer. The preferred monomer composition (mol %) of the electrolyte polymer precursor is TFE:vinyl ether = (50-99): (50-1), and more preferably TFE:vinyl ether = (50-93): (50-7).

[1049] The electrolyte polymer precursor may be modified with a third monomer in an amount of 0 to 20% by mass of all monomers. Examples of the third monomer include polyfunctional monomers such as CTFE, vinylidene fluoride, perfluoroalkyl vinyl ether, and divinylbenzene.

[1050] The electrolyte polymer precursor thus obtained can be formed into a film, for example, and then subjected to hydrolysis with an alkaline solution and treatment with an inorganic acid to be used as a polymer electrolyte membrane for fuel cells, electrolysis devices, redox flow batteries, and the like.

[1051] Alternatively, the electrolyte polymer dispersion may be obtained by performing hydrolysis with an alkali solution while maintaining the dispersed state of the electrolyte polymer precursor.

[1052] Next, by heating to 120° C. or higher in a pressure container, the material can be dissolved in, for example, a water / alcohol mixed solvent to form a solution.

[1053] The solution thus obtained can be used as, for example, a binder for an electrode, or can be compounded with various additives and cast to form a film, and used in, for example, an antifouling coating film, an organic actuator, and the like.

[1054] (5) TFE / VDF copolymer

[1055] In the production method of the present invention, the polymerization temperature of the TFE / VDF copolymer is not particularly limited and may be 0 to 100° C. The polymerization pressure is appropriately determined depending on other polymerization conditions such as the polymerization temperature and may generally be 0 to 9.8 MPaG.

[1056] The preferred monomer composition (mol%) of the TFE / VDF copolymer is TFE:VDF=(5-90):(95-10). As the TFE / VDF copolymer, a third monomer may be further used to modify the copolymer in the range of 0-50 mol% of the total monomers. Preferably, TFE:ethylene:third monomer=(30-85):(10-69.9):(0.1-10).

[1057] As the third monomer, preferably

[1058] Type: CX 11 X 12 =CX 13 (CX 14 X15 ) n11 X 16

[1059] (Where X 11 ~X 16 are the same or different, represents H, F or Cl, and n11 represents an integer from 0 to 8. TFE and VDF are not included, or

[1060] Type: CX 21 X 22 =CX 23 -O(CX 24 X 25 ) n21 X 26

[1061] (Where X 21 ~X 26 are the same or different, represent H, F or Cl, and n21 represents an integer of 0 to 8).

[1062] In addition, the third monomer may be a non-fluorinated ethylenic monomer. From the aspect of maintaining heat resistance and chemical resistance, the non-fluorinated ethylenic monomer is preferably selected from ethylenic monomers having a carbon number of 6 or less. Examples thereof include ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, alkyl vinyl ethers (methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc.), maleic acid, itaconic acid, 3-butenoic acid, 4-pentenoic acid, vinyl sulfonic acid, acrylic acid, methacrylic acid, etc.

[1063] In the polymerization of the TFE / VDF copolymer, the polymer (I) can be used within the range of use in the production method of the present invention, and is usually added in an amount of 0.0001% by mass to 5% by mass based on 100% by mass of the aqueous medium.

[1064] The TFE / VDF copolymer obtained by polymerization can be amidated by contacting it with ammonia water, ammonia gas or a nitrogen compound that can generate ammonia.

[1065] The TFE / VDF copolymer obtained by the above method is also preferably used as a raw material for obtaining TFE / VDF copolymer fibers by a spinning and stretching method. The above spinning and stretching method refers to the following method: the TFE / VDF copolymer is melt-spun and then cooled and solidified to obtain undrawn yarns, and then the undrawn yarns are made to run in a heated cylinder and stretched to obtain TFE / VDF copolymer fibers.

[1066] The TFE / VDF copolymer may also be dissolved in an organic solvent to obtain a solution of the TFE / VDF copolymer. Examples of the organic solvent include nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethylformamide; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as tetrahydrofuran and dioxane; and low-boiling-point general-purpose organic solvents such as mixed solvents thereof. The solution may be used as a binder for a battery.

[1067] It is also preferred that the aqueous dispersion of the above-mentioned TFE / VDF copolymer is coated on a porous substrate consisting of a polyolefin resin and used as a composite porous membrane. It is also preferred that inorganic particles and / or organic particles are dispersed in an aqueous dispersion and coated on a porous substrate and used as a composite porous membrane. The composite porous membrane obtained in this way can be used as a separator of a lithium secondary battery, etc.

[1068] The above-mentioned melt-processable fluororesin powder can be used as a powder coating. When the powder coating composed of the above-mentioned melt-processable fluororesin powder is applied to a substrate, a coating with a smooth surface can be obtained. The melt-processable fluororesin powder with an average particle size of 1 μm or more and less than 100 μm is particularly suitable as a powder coating used in electrostatic coating, and the melt-processable fluororesin powder with an average particle size of 100 μm or more and 1000 μm or less is particularly suitable as a powder coating used in spin coating or spin molding.

[1069] The melt-processable fluororesin powder can be produced by drying and powderizing the melt-processable fluororesin obtained by the production method of the present invention. A production method for producing the melt-processable fluororesin powder is also one of the present invention.

[1070] (III) Fluororubber

[1071] In the manufacturing method of the present invention, regarding the polymerization of the above-mentioned fluororubber, pure water and polymer (I) are added to a pressure-resistant reaction vessel equipped with a stirrer, and monomers are added after deoxidation to make it reach a specified temperature, and a polymerization initiator is added to initiate the reaction. Since the pressure decreases as the reaction proceeds, in order to maintain the initial pressure, additional monomers are continuously or intermittently supplied. At the moment when a specified amount of monomers is supplied, the supply is stopped, the monomers in the reaction vessel are purged, the temperature is restored to room temperature, and the reaction is terminated. In this case, the polymer emulsion can be continuously taken out from the reaction vessel.

[1072] In particular, when manufacturing a thermoplastic elastomer as the above-mentioned fluororubber, as disclosed in International Publication No. 00 / 01741, the following method can also be used: fluorine-containing polymer particles are temporarily synthesized at the above-mentioned higher concentration, and then diluted and further polymerized, thereby accelerating the final polymerization rate compared to the usual polymerization.

[1073] In the polymerization of the fluororubber, appropriate conditions are selected from the aspects of the physical properties of the target polymer and the control of the polymerization rate, and the polymerization temperature is usually -20°C to 200°C, preferably 5°C to 150°C, and the polymerization pressure is usually 0.5MPaG to 10MPaG, preferably 1MPaG to 7MPaG. In addition, the pH in the polymerization medium is preferably maintained at 2.5 to 13 using a pH adjuster described later by a known method.

[1074] As the monomer used in the polymerization of the above-mentioned fluororubber, in addition to vinylidene fluoride, fluorine-containing ethylenically unsaturated monomers having at least the same number of fluorine atoms as carbon atoms and copolymerizable with vinylidene fluoride can also be cited. As the above-mentioned fluorine-containing ethylenically unsaturated monomers, trifluoropropylene, pentafluoropropylene, hexafluorobutene, octafluorobutene can be cited. Among them, hexafluoropropylene is particularly suitable for the reason of the elastomeric properties obtained when it blocks the crystal growth of the polymer. As the above-mentioned fluorine-containing ethylenically unsaturated monomers, trifluoroethylene, TFE and CTFE etc. can also be cited, and 1 or more fluorine-containing monomers with chlorine and / or bromine substituents can also be used. Perfluoro (alkyl vinyl ether), such as perfluoro (methyl vinyl ether) can also be used. TFE and HFP are preferred in the manufacture of fluororubber.

[1075] A preferred monomer composition (mass %) of the fluororubber is vinylidene fluoride:HFP:TFE=(20 to 70):(30 to 48):(0 to 32). The fluororubber having such a composition exhibits excellent elastomeric properties, chemical resistance, and thermal stability.

[1076] In the polymerization of the fluororubber, the polymer (I) can be used within the range of use in the production method of the present invention and is usually added in an amount of 0.0001 to 20% by mass relative to 100% by mass of the aqueous medium, preferably 10% by mass or less, more preferably 2% by mass or less.

[1077] In the polymerization of the above-mentioned fluororubber, as a polymerization initiator, a known inorganic free radical polymerization initiator can be used. As the above-mentioned inorganic free radical polymerization initiator, the existing known water-soluble inorganic peroxides, such as persulfates, perphosphates, perborate, percarbonate or permanganate of sodium, potassium and ammonium are particularly useful. The above-mentioned free radical polymerization initiator can also be further activated by a reducing agent (such as sulfite, bisulfite, pyrosulfite, hyposulfite, thiosulfate, phosphite or hypophosphite of sodium, potassium or ammonium), or by an easily oxidizable metal compound (such as ferrous salt, cuprous salt or silver salt). Suitable inorganic free radical polymerization initiator is ammonium persulfate, and more preferably ammonium persulfate and sodium bisulfite are used simultaneously in a redox system.

[1078] The added concentration of the polymerization initiator is appropriately determined depending on the molecular weight of the target fluorinated polymer and the polymerization reaction rate, and is set to 0.0001 to 10 mass %, preferably 0.01 to 5 mass %, based on 100 mass % of the total monomer amount.

[1079] In the polymerization of the above-mentioned fluororubber, known substances can be used as chain transfer agents, and hydrocarbons, esters, ethers, alcohols, ketones, chlorides, carbonates, etc. can be used. In the case of thermoplastic elastomers, hydrocarbons, esters, ethers, alcohols, chlorides, iodides, etc. can be used. Among them, acetone and isopropanol are preferred; in the polymerization of thermoplastic elastomers, isopentane, diethyl malonate and ethyl acetate are preferred from the aspect of not easily reducing the reaction rate; I(CF) is preferred from the aspect of being able to iodinate the polymer terminal and being able to be used as a reactive polymer. 2 ) 4 I, I (CF 2 ) 6 I. ICH 2 I and other diiodide compounds.

[1080] The amount of the chain transfer agent used is preferably usually 0.5×10 -3 Mole %~5×10 -3 mol%, preferably 1.0×10 -3 Mole %~3.5×10 -3 Mol %.

[1081] In the polymerization of the fluororubber, paraffin wax or the like can be preferably used as an emulsion stabilizer, and in the polymerization of the thermoplastic elastomer, phosphate, sodium hydroxide, potassium hydroxide or the like can be preferably used as a pH adjuster.

[1082] The fluororubber obtained by the production method of the present invention has a solid content concentration of 1.0 to 40% by mass at the time of polymerization termination, an average particle size of 0.03 to 1 μm, preferably 0.05 to 0.5 μm, and a number average molecular weight of 1,000 to 2,000,000.

[1083] The fluororubber obtained by the production method of the present invention can be prepared into a dispersion suitable for rubber molding by adding a dispersion stabilizer such as a hydrocarbon surfactant, concentrating, etc. as needed. The above dispersion is treated by pH adjustment, coagulation, heating, etc. Each treatment is performed as follows.

[1084] The pH adjustment includes adding an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid and / or a carboxylic acid having 5 or less carbon atoms and pK=4.2 or less to adjust the pH to 2 or less.

[1085] The above coagulation is performed by adding an alkaline earth metal salt. Examples of the above alkaline earth metal salt include nitrates, chlorates, and acetates of calcium or magnesium.

[1086] Of the pH adjustment and the coagulation, either one may be performed first, but the pH adjustment is preferably performed first.

[1087] Among fluororubbers, perfluororubber is obtained by polymerizing a perfluoromonomer in an aqueous medium in the presence of the polymer (I).

[1088] As the perfluoromonomer, it is preferred to be selected from

[1089] Tetrafluoroethylene [TFE],

[1090] Hexafluoropropylene [HFP],

[1091] General formula: CF 2 =CF-ORf 13

[1092] (Where Rf 13 represents a perfluoroalkyl group having 1 to 8 carbon atoms),

[1093] General formula: CF 2 =CFOCF 2 O 14

[1094] (Where Rf 14 A fluorinated monomer represented by a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms and containing 1 to 3 oxygen atoms; and

[1095] General formula: CF 2 =CFO(CF2 CF(Y 15 )O) m (CF 2 ) n F

[1096] (Where Y 15 represents a fluorine atom or a trifluoromethyl group. m is an integer of 1 to 4. n is an integer of 1 to 4) is at least one member selected from the group consisting of fluorine-containing monomers.

[1097] In the polymerization of the perfluoromonomer, a monomer providing a crosslinking site may be polymerized together with the perfluoromonomer.

[1098] The ion exchange capacity of the polymer (I) used in the method for producing the perfluoroelastomer is preferably 1.50 meq / g or more. The ion exchange capacity of the polymer (I) is preferably 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.40 meq / g or more, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, and 3.50 meq / g or more. The ion exchange capacity is the content of the ionic group (anionic group) of the polymer (I), and is calculated from the composition of the polymer (I). In order to determine the ion exchange capacity, the precursor group (e.g., -COOCH 3 ) are not considered as ionic groups. When the ion exchange capacity of polymer (I) is higher, the anionic groups of polymer (I) are more, particles with high stability are formed, and the particle forming power is high, so the number of particles per unit amount of water increases, and it is estimated that the polymerization rate is higher. If the ion exchange capacity of polymer (I) is too low, the perfluoroelastomer produced by polymerization adheres to the polymerization reactor, or a sufficient polymerization rate cannot be obtained, or the number of perfluoroelastomer particles produced is reduced.

[1099] The amount of polymer (I) added is preferably 0.01% to 20% by mass relative to 100% by mass of the aqueous medium. By making the amount of polymer (I) added (amount present) in the above polymerization within the above range, the polymerization reaction of the perfluoromonomer proceeds smoothly, and the perfluoroelastomer can be efficiently manufactured. If the amount of polymer (I) added is too small, a sufficient polymerization rate cannot be obtained, or a sufficient yield cannot be obtained.

[1100] The amount of polymer (I) added is more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, particularly preferably 0.75% by mass or more, and most preferably 1.0% by mass or more, relative to 100% by mass of the aqueous medium, because the polymerization reaction of the perfluoromonomer proceeds more smoothly.

[1101] In addition, if the amount of polymer (I) added is too much, an effect commensurate with the amount added cannot be obtained, which is economically disadvantageous. In addition, since post-treatment after the termination of polymerization may become complicated, it is more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less relative to 100% by mass of the aqueous medium.

[1102] The polymerization of the perfluoromonomer can also be carried out in the presence of a polymerization initiator. The polymerization initiator is as described above. The amount of the polymerization initiator added is preferably 0.0001% to 10% by mass, and more preferably 0.01% to 5% by mass, relative to 100% by mass of the perfluoromonomer. By making the amount of the polymerization initiator added (the amount present) in the above-mentioned polymerization within the above-mentioned range, the polymerization reaction of the perfluoromonomer proceeds smoothly, and the perfluoroelastomer can be efficiently manufactured. If the amount of the polymerization initiator added is too small, a sufficient polymerization rate cannot be obtained, or a sufficient yield cannot be obtained.

[1103] The polymerization of the perfluoromonomer may also be carried out in the presence of a pH adjuster. By carrying out the polymerization in the presence of a pH adjuster, the adhesion of the perfluoroelastomer to the polymerization reactor can be further suppressed, and a sufficient number of perfluoroelastomer particles can be produced at a sufficient polymerization rate. The pH adjuster may be added before or after the start of the polymerization.

[1104] As the pH adjuster, 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.

[1105] The partially fluorinated rubber among the fluororubbers is obtained by polymerizing a fluorine-containing monomer in an aqueous medium in the presence of the polymer (I).

[1106] As the fluorine-containing monomer for obtaining the partially fluorinated rubber, it is preferred to select from vinylidene fluoride (vinylidene fluoride) (VdF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl fluoride, iodine-containing fluorovinyl ether, general formula: CHX 1 =CX 2 Rf(where X 1 and X 2 One of them is H and the other is F, and Rf is at least one member selected from the group consisting of fluorinated monomers (2) represented by a linear or branched fluorinated alkyl group having 1 to 12 carbon atoms.

[1107] In the method for producing a partially fluorinated rubber, it is preferred that at least vinylidene fluoride or tetrafluoroethylene is polymerized as the fluorine-containing monomer, and it is more preferred that vinylidene fluoride is polymerized.

[1108] The amount of polymer (I) added is preferably 0.01% to 20% by mass relative to 100% by mass of the aqueous medium. By making the amount of polymer (I) added (amount present) in the above polymerization within the above range, the polymerization reaction of the fluorinated monomer proceeds smoothly, and partially fluorinated rubber can be efficiently produced. If the amount of polymer (I) added is too small, sufficient polymerization rate cannot be obtained, or sufficient yield cannot be obtained.

[1109] The amount of polymer (I) added is more preferably 0.0001% by mass or more, further preferably 0.0005% by mass or more, further preferably 0.001% by mass or more, particularly preferably 0.005% by mass or more, and most preferably 0.01% by mass or more, relative to 100% by mass of the aqueous medium, since the polymerization reaction of the fluorinated monomer proceeds more smoothly.

[1110] In addition, if the amount of polymer (I) added is too much, an effect commensurate with the amount added cannot be obtained, which is economically disadvantageous. Therefore, it is more preferably 2 mass% or less, further preferably 1 mass% or less, and particularly preferably 0.5 mass% or less relative to 100 mass% of the aqueous medium.

[1111] The polymerization of the fluorinated monomer can also be carried out in the presence of a polymerization initiator. The polymerization initiator is as described above. The amount of the polymerization initiator is appropriately determined according to the type of monomer, the molecular weight of the target partially fluorinated rubber, and the reaction rate. The amount of the polymerization initiator is appropriately determined according to the molecular weight of the target partially fluorinated rubber and the polymerization reaction rate, and is preferably 0.00001% to 10% by mass, and more preferably 0.0001% to 1% by mass, relative to 100% by mass of the total monomer amount.

[1112] After each operation, the fluororubber is washed with water of the same volume as the fluororubber to remove a small amount of impurities such as buffer and salt in the fluororubber, and then dried. Drying is usually performed in a drying furnace at a high temperature of about 70°C to 200°C while circulating air.

[1113] The fluororubber may be a partially fluorinated rubber or a perfluororubber.

[1114] The partially fluorinated rubber preferably contains methylene groups (-CH 2 -). As the main chain contains -CH 2 - partially fluorinated rubber, as long as it contains -CH 2 The chemical structure represented by - is not particularly limited, and examples thereof include -CH 2-CF 2 -、-CH 2 -CH(CH 3 )-、-CH 2 -CH 2 - Partially fluorinated rubbers with structures such as fluorinated rubbers, which can be introduced into the main chain of the partially fluorinated rubber by polymerizing vinylidene fluoride, propylene, ethylene, etc. The content of tetrafluoroethylene units in the partially fluorinated rubber (the content of the polymerized units based on tetrafluoroethylene relative to the total polymerized units of the partially fluorinated rubber) can be less than 40 mol%.

[1115] As the partially fluorinated rubber, for example, it is preferred to contain a compound selected from tetrafluoroethylene (TFE), vinylidene fluoride (VdF) and a compound of the general formula: CF 2 =CF-Rf a (Where Rf a For-CF 3 OR-ORf b (Rf b The partially fluorinated rubber preferably contains a VdF unit or a TFE unit.

[1116] As the partially fluorinated rubber, there can be mentioned vinylidene fluoride (VdF) based fluororubber, tetrafluoroethylene (TFE) / propylene (Pr) based fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) based fluororubber, ethylene / hexafluoropropylene (HFP) based fluororubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) based fluororubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) based fluororubber, etc. Among them, at least one selected from the group consisting of vinylidene fluoride based fluororubber and tetrafluoroethylene / propylene based fluororubber is preferred.

[1117] The above-mentioned vinylidene fluoride-based fluororubber is preferably a copolymer composed of 45 mol% to 85 mol% of vinylidene fluoride and 55 mol% to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. More preferably, it is a copolymer composed of 50 mol% to 80 mol% of vinylidene fluoride and 50 mol% to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

[1118] Examples of the at least one other monomer copolymerizable with vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl fluoride, general formula (100): CHX101 =CX 102 R 101 (Where X 101 and X 102 One of them is H and the other is F, Rf 101 is a fluorinated monomer represented by a linear or branched fluoroalkyl group having 1 to 12 carbon atoms, general formula (170): CH 2 =CH-(CF 2 ) n -X 171 (Where X 171 is H or F, n is an integer of 3 to 10), monomers such as monomers providing crosslinking sites; non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ether. They can be used alone or in any combination. Among these, it is preferred to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE. As the fluoroalkyl vinyl ether, the fluorinated monomer represented by the general formula (160) is preferred.

[1119] Specific examples of vinylidene fluoride-based fluororubbers include VdF / HFP-based rubbers, VdF / HFP / TFE-based rubbers, VdF / CTFE-based rubbers, VdF / CTFE / TFE-based rubbers, VDF / fluorinated monomer-based rubbers represented by the general formula (100), VDF / fluorinated monomer-based rubbers represented by the general formula (100) / TFE-based rubbers, VDF / perfluoro(methyl vinyl ether) [PMVE]-based rubbers, VDF / PMVE / TFE-based rubbers, and VDF / PMVE / TFE / HFP-based rubbers. As the VDF / fluorinated monomer-based rubber represented by the general formula (100), VDF / CH 2 =CFCF 3 The VDF / fluorinated monomer / TFE rubber is preferably VDF / TFE / CH 2 =CFCF 3 It is made of rubber.

[1120] As the vinylidene fluoride-based fluororubber, a VdF / HFP copolymer or a VdF / HFP / TFE copolymer is more preferred, and a composition of VdF / HFP / TFE of (32 to 85) / (10 to 34) / (0 to 40) (mol %) is particularly preferred. As the composition of VdF / HFP / TFE, (32 to 85) / (15 to 34) / (0 to 34) (mol %) is more preferred, and (47 to 81) / (17 to 32) / (0 to 26) (mol %) is further preferred.

[1121] For example, in the above-mentioned VdF / HFP copolymer, the composition of VdF / HFP is preferably (45-85) / (15-55) (mol %), more preferably (50-83) / (17-50) (mol %), further preferably (55-81) / (19-45) (mol %), and particularly preferably (60-80) / (20-40) (mol %).

[1122] The above VDF / CH 2 =CFCF 3 The rubber is preferably composed of 40 mol% to 99.5 mol% of VDF and CH 2 =CFCF 3 A copolymer composed of 0.5 mol% to 60 mol%, more preferably 50 mol% to 85 mol% of VDF and CH 2 =CFCF 3 A copolymer composed of 20 mol% to 50 mol%.

[1123] The tetrafluoroethylene / propylene fluororubber is preferably a copolymer composed of 45 mol% to 70 mol% of tetrafluoroethylene, 55 mol% to 30 mol% of propylene, and 0 to 5 mol% of a fluorine-containing monomer providing a crosslinking site.

[1124] The fluororubber may be a perfluororubber. The perfluororubber is preferably a perfluororubber containing TFE, for example, preferably at least one selected from the group consisting of a copolymer of TFE / a fluorinated monomer represented by the general formula (160), (130) or (140) and a copolymer of TFE / a fluorinated monomer represented by the general formula (160), (130) or (140) / a monomer providing a crosslinking site.

[1125] The composition thereof is preferably 45 to 90 / 10 to 55 (mol %), more preferably 55 to 80 / 20 to 45, and even more preferably 55 to 70 / 30 to 45 in the case of a TFE / PMVE copolymer.

[1126] In the case of a copolymer of TFE / PMVE / a monomer providing a crosslinking site, it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol %), more preferably 55 to 77.9 / 20 to 49.9 / 0.1 to 3.5, and further preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.

[1127] In the case of a copolymer of TFE / a fluorinated monomer having 4 to 12 carbon atoms and represented by the general formula (160), (130) or (140), the ratio is preferably 50 to 90 / 10 to 50 (mol %), more preferably 60 to 88 / 12 to 40, further preferably 65 to 85 / 15 to 35.

[1128] In the case of a copolymer of TFE / a fluorinated monomer represented by the general formula (160), (130) or (140) having 4 to 12 carbon atoms / a monomer providing a crosslinking site, the ratio is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol %), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and still more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3.

[1129] Outside this composition range, the properties as a rubber elastic body are lost and the properties close to those of a resin tend to be exhibited.

[1130] The above-mentioned perfluororubber is preferably at least one selected from the group consisting of a copolymer of TFE / fluorinated monomer represented by the general formula (140) / fluorinated monomer providing cross-linking sites, a copolymer of TFE / perfluorovinyl ether represented by the general formula (140), a copolymer of TFE / fluorinated monomer represented by the general formula (160) and a copolymer of TFE / fluorinated monomer represented by the general formula (160) / monomer providing cross-linking sites.

[1131] Examples of the perfluororubber include perfluororubbers described in International Publication No. 97 / 24381, Japanese Examined Patent Publication No. 61-57324, Japanese Examined Patent Publication No. 4-81608, and Japanese Examined Patent Publication No. 5-13961.

[1132] The glass transition temperature of the fluororubber is preferably -70°C or higher, more preferably -60°C or higher, and further preferably -50°C or higher, from the perspective of excellent compression set at high temperatures. In addition, from the perspective of good cold resistance, it is preferably 5°C or lower, more preferably 0°C or lower, and further preferably -3°C or lower.

[1133] The above-mentioned glass transition temperature can be calculated as follows: using a differential scanning calorimeter (manufactured ...

Claims

1. A method for producing a fluorine-containing polymer, comprising: A step of polymerizing a monomer (I) represented by the general formula (I) in an aqueous medium in the substantial absence of a fluorinated surfactant, thereby obtaining a crude composition containing a polymer of the monomer (I), wherein the fluorinated surfactant does not include the monomer (I) represented by the general formula (I); A step of removing dimers and trimers of the monomer (I) contained in the crude composition from the crude composition to obtain a polymer (I) having a content of dimers and trimers of the monomer (I) of 1.0% by mass or less relative to the polymer (I); and a step of polymerizing a fluorinated monomer in an aqueous medium in the presence of the polymer (I) to obtain a fluorinated polymer, CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) Where, X 1 and X 3 Each independently is F, Cl, H or CF3; X 2 is H, F, alkyl or fluorinated alkyl; A 0 is an anionic group; R is a connecting group; Z 1 and Z 2 Each is independently H, F, an alkyl group or a fluorinated alkyl group; and m is an integer greater than 1.

2. The manufacturing method according to claim 1, wherein: The molecular weight of the monomer (I) is 500 or less.

3. The manufacturing method according to claim 1 or 2, wherein: A 0 is -COOM, -SO3M, -OSO3M or -C(CF3)2OM, M is -H, metal atom, -NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

4. The production method according to any one of claims 1 to 3, wherein A 0 is -COOM, M is -H, metal atom, -NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

5. The production method according to any one of claims 1 to 4, wherein Monomer (I) is a monomer represented by general formula (1), CX2=CY(-CZ2-O-Rf-A) (1) In the formula, X is the same or different and is -H or F, Y is -H, -F, alkyl or fluorinated alkyl, Z is the same or different and is -H, -F, alkyl or fluorinated alkyl; 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. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group; wherein at least one of X, Y and Z contains a fluorine atom.

6. The production method according to any one of claims 1 to 5, wherein Monomer (I) is a monomer represented by general formula (1A), CH2=CF(-CF2-O-Rf-A)(1A) In the formula, 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, and M is -H, a metal atom, -NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

7. The manufacturing method according to claim 5 or 6, wherein: A is -COOM, M is -H, metal atom, -NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

8. The production method according to any one of claims 1 to 7, wherein Dimers and trimers of monomer (I) are removed from the crude composition by ultrafiltration of the crude composition.

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