Method for producing fluoropolymers

Abstract

To provide a method for producing a novel fluoropolymer.SOLUTION: There is provided a method for producing a fluoropolymer which comprises a step of polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing a polymerization unit (1) based on a monomer represented by the following general formula (1). CX2=CY(-CZ2-O-Rf-A) (1) (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group, Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR74, an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent, R7 is H or an organic group. Provided that at least one of X, Y and Z is a fluorine atom.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a fluoropolymer. [Background technology]

[0002] The use of certain fluorine-containing polymers in the production of fluoropolymers by emulsion polymerization is known.

[0003] For example, Patent Document 1 describes a method for producing an aqueous dispersion containing rod-shaped microparticles of polytetrafluoroethylene having an average aspect ratio of 2 or more, which is characterized by polymerizing tetrafluoroethylene in the presence of a polymer consisting of polymerization units represented by formula 1, or a copolymer consisting of polymerization units represented by formula 1 and polymerization units represented by formula 2 (wherein the polymerization units represented by formula 1 account for 40 mol % or more of the total polymerization units). [ka] -CF2CFX- ...Formula 2 However, in formula 1, R f represents a perfluoroperfluoroalkylene group having 1 to 6 carbon atoms, M represents an alkali metal ion or an ammonium ion, and in formula 2, X represents a fluorine atom or a chlorine atom. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-181009 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure aims to provide a novel method for producing fluoropolymers. [Means for solving the problem]

[0006] The present disclosure relates to a method for producing a fluoropolymer, comprising the step of polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing polymerization units (1) based on a monomer represented by the following general formula (1) to obtain a fluoropolymer: CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom. In the above general formula (1), it is preferable that at least one of X is -H. It is also preferable that both of X are -H in the general formula (1). In the above general formula (1), Rf is preferably a fluorine-containing alkylene group having 1 to 10 carbon atoms, or a fluorine-containing alkylene group having 2 to 12 carbon atoms and an ether bond. The above polymerized units (1) are preferably polymerized units (1A) based on a monomer represented by the following general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.) The polymerized units (1) are also preferably polymerized units (1a) based on a fluoroallyl ether compound represented by the following general formula (1a). CX2 = CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-A (1a) (In the formula, each X is the same and represents F or H; n5 represents 0 or an integer of 1 to 10; and A is as defined above.) In the above formula, A is preferably -COOM. Also, in the above formula, M is preferably -H, -Na, -K, -Li or -NH4. The polymer (1) preferably has a content of polymerized units (1) of 90 mol % or more based on the total polymerized units. The number average molecular weight of the polymer (1) is 1.0×10 4 More preferably, it is 3.0×10 4 More preferably, it is equal to or greater than this. The fluoropolymer is preferably polytetrafluoroethylene, and the polyfluorotetraethylene is preferably modified polytetrafluoroethylene. The present disclosure also relates to a method for producing an extruded body, comprising the step of extruding the polytetrafluoroethylene obtained by the above-mentioned production method.

[0007] The present disclosure further relates to a composition comprising a fluoropolymer and a polymer (1) including polymerized units (1) based on a monomer represented by the following general formula (1): CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom. The above polymerized units (1) are preferably polymerized units (1A) based on a monomer represented by the following general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.) In the composition of the present disclosure, the content of the polymer (1) is preferably from 0.0001% by mass to 20% by mass relative to the fluoropolymer. Preferably, the fluoropolymer is polytetrafluoroethylene. The polyfluorotetraethylene is preferably a modified polytetrafluoroethylene. The compositions of the present disclosure are preferably extensible. The composition of the present disclosure preferably has a breaking strength of 10.0 N or more. The composition of the present disclosure is preferably substantially free of fluorine-containing surfactant. The compositions of the present disclosure are preferably in the form of a powder. Effect of the Invention

[0008] The manufacturing process of the present disclosure is a novel method for producing fluoropolymers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Before specifically describing the present disclosure, some terms used herein will be defined or explained.

[0010] In this specification, a fluororesin is a partially crystalline fluoropolymer, i.e., a fluoroplastic. A fluororesin has a melting point and is thermoplastic, but may be melt-processable or non-melt-processable.

[0011] In this specification, melt processability means that the polymer can be melted and processed using conventional processing equipment such as an extruder, an injection molding machine, etc. Therefore, a melt processable fluororesin usually has a melt flow rate of 0.01 to 500 g / 10 min, as measured by the measurement method described below.

[0012] In this specification, fluororubber is an amorphous fluoropolymer. "Amorphous" means that the magnitude of the melting peak (ΔH) that appears 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 4.5 J / g or less. Fluororubber exhibits elastomeric properties by crosslinking. Elastomeric properties refer to the property that the polymer can be stretched and can retain its original length when the force required to stretch the polymer is no longer applied.

[0013] In this specification, the partially fluorinated rubber is a fluoropolymer that contains fluoromonomer units and has a perfluoromonomer unit content of less than 90 mol% relative to all polymerized units, has a glass transition temperature of 20°C or lower, and has a melting peak (ΔH) magnitude of 4.5 J / g or less.

[0014] In this specification, perfluororubber is a fluoropolymer having a perfluoromonomer unit content of 90 mol% or more relative to the total polymerized units, a glass transition temperature of 20°C or less, a melting peak (ΔH) of 4.5 J / g or less, and a fluorine atom concentration of 71 mass% or more. In this specification, the concentration of fluorine atoms in the fluoropolymer is calculated from the type and content of each monomer constituting the fluoropolymer to determine the concentration of fluorine atoms (mass%) in the fluoropolymer.

[0015] In this specification, a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule. The perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atom are replaced with chlorine atoms, in addition to carbon atoms and fluorine atoms, and may also have nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, or silicon atoms in addition to carbon atoms. The perfluoromonomer is preferably a monomer in which all hydrogen atoms are replaced with fluorine atoms. The perfluoromonomer does not include a monomer that provides a crosslinking site.

[0016] The monomer that provides a crosslinking site is a monomer (cure site monomer) having a crosslinkable group that provides the fluoropolymer with a crosslinking site for forming a crosslink with a curing agent.

[0017] In this specification, polytetrafluoroethylene [PTFE] is preferably a fluoropolymer having a tetrafluoroethylene content of 99 mol % or more relative to all polymerized units.

[0018] In this specification, both the fluororesin (excluding polytetrafluoroethylene) and the fluororubber are preferably fluoropolymers having a tetrafluoroethylene content of less than 99 mol % relative to the total polymerized units.

[0019] In this specification, the content of each monomer constituting the fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and other known methods depending on the type of monomer.

[0020] As used herein, "organic group" means a group containing one or more carbon atoms or a group formed by removing a hydrogen atom from an organic compound. Examples of the "organic group" are: an alkyl group which may have one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group which may have one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents, Cyano group, Formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2- and RaNRbSO2- (In these formulas, Ra is independently an alkyl group which may have one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group which may have one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents, Rb is independently H or an alkyl group which may have one or more substituents. Includes: The organic group is preferably an alkyl group which may have one or more substituents.

[0021] In the present specification, the term "substituent" means a substitutable group. 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 sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an aromatic aryl ... These include an aryl 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 thio group, an aromatic thio group, a hydroxy group, a cyano group, a sulfo group, a carboxy 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.

[0022] The aliphatic group may be saturated or unsaturated, and may have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic group include alkyl groups having a total of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc.

[0023] 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 thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include aryl groups 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-methanesulfonylphenyl group.

[0024] The heterocyclic group may have a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the heterocyclic group include a 5- or 6-membered heterocycle having a total of 2 to 12, preferably 2 to 10, carbon atoms, such as a 2-tetrahydrofuryl group, a 2-pyrimidyl group, etc.

[0025] The acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the acyl group include acyl groups having a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

[0026] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the acylamino group include an acylamino group having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and an alkylcarbonylamino group having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0027] The aliphatic oxycarbonyl group may be saturated or unsaturated, and may have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic oxycarbonyl group include alkoxycarbonyl groups having a total of 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and (t)-butoxycarbonyl groups.

[0028] 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, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, and an N-phenylcarbamoyl group.

[0029] The aliphatic sulfonyl group may be saturated or unsaturated and may have a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic sulfonyl group include alkylsulfonyl groups having a total of 1 to 6 carbon atoms, preferably a total of 1 to 4 carbon atoms, such as methanesulfonyl.

[0030] The aromatic sulfonyl group may have a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic sulfonyl group include arylsulfonyl groups having a total of 6 to 10 carbon atoms, such as benzenesulfonyl.

[0031] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

[0032] The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the acylamino group include an acylamino group having a total of 2 to 12 carbon atoms, preferably a total of 2 to 8 carbon atoms, and more preferably an alkylcarbonylamino group having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0033] The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, or a 2-pyridinesulfonamide group.

[0034] 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 a total of 1 to 9 carbon atoms, a dialkylsulfamoyl group having a total of 2 to 10 carbon atoms, an arylsulfamoyl group having a total of 7 to 13 carbon atoms, and a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkylsulfamoyl group having a total of 1 to 7 carbon atoms, a dialkylsulfamoyl group having a total of 3 to 6 carbon atoms, an arylsulfamoyl group having a total of 6 to 11 carbon atoms, and a heterocyclic sulfamoyl group having a total of 2 to 10 carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, and a 4-pyridine sulfamoyl group.

[0035] The aliphatic oxy group may be saturated or unsaturated and may have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. Examples of the aliphatic oxy group include an alkoxy group having a total of 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc.

[0036] 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 aryl group, or an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0037] The aliphatic thio group may be saturated or unsaturated and is an alkylthio group having a total of 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group, a carbamoylmethylthio group, or a t-butylthio group.

[0038] The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 9 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 10 carbon atoms, an arylcarbamoylamino group having a total of 7 to 13 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 12 carbon atoms, preferably a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 7 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 6 carbon atoms, an arylcarbamoylamino group having a total of 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 10 carbon atoms, such as a carbamoylamino group, a methylcarbamoylamino group, an N,N-dimethylcarbamoylamino group, a phenylcarbamoylamino group, and a 4-pyridinecarbamoylamino group.

[0039] Further herein, ranges expressed by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0040] Further, as used herein, references to "at least 1" include all numbers greater than or equal to 1 (e.g., 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.).

[0041] Next, the method for producing the fluoropolymer of the present disclosure will be specifically described.

[0042] The present disclosure relates to a method for producing a fluoropolymer, comprising the step of polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing polymerization units (1) based on a monomer represented by the following general formula (1) to obtain a fluoropolymer: CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom. The production method of the present disclosure can stably and efficiently produce a fluoropolymer by using the above polymer (1), and can also produce a high molecular weight fluoropolymer in high yield.

[0043] In the above general formula (1), X is -H or -F. Both X's may be -F, or at least one X may be -H. For example, one X may be -F and the other may be -H, or both X's may be -H.

[0044] In the above general formula (1), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group containing no fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has a carbon number of at most 6, more preferably at most 4, and even more preferably at most 3. The above-mentioned fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the carbon number may be at least 1. The above-mentioned fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less carbon atoms. The above Y is preferably -H, -F or -CF3, and more preferably -F.

[0045] In the above general formula (1), Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. The alkyl group is an alkyl group containing no fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has a carbon number of at most 6, more preferably at most 4, and even more preferably at most 3. The above-mentioned fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the carbon number may be at least 1. The above-mentioned fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less carbon atoms. The above Z is preferably -H, -F or -CF3, and more preferably -F.

[0046] In the above 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.

[0047] In the above general formula (1), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not include a structure in which an oxygen atom is at the terminal, and contains an ether bond between carbon atoms. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. Also, the number is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0048] The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more, and more preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less. For example, the following formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is H, F or CF3; p1+q1+r1 are integers from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, except for Z 3 and Z 4 When both are H, p1+q1+r1+s1 is not 0). Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)- (wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF(CF3)CH2- and the like. The above-mentioned fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0049] In the above general formula (1), A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group. R 7 As the 1-10 is preferably an organic group represented by the formula: 1-4 More preferred is an organic group represented by the formula: 1-4 More preferred are alkyl groups of the formula: The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li. The above M is -H, a metal atom, or -NR 7 4 is preferred, and -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7 4 is more preferred, -H, -Na, -K, -Li or -NH4 is even more preferred, -Na, -K or -NH4 is even more preferred, -Na or -NH4 is especially preferred, and -NH4 is most preferred. The above A is preferably -COOM or -SO3M, and more preferably -COOM.

[0050] The monomer represented by the general formula (1) may, for example, be a monomer represented by the following formula (1a): CX2 = CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-A (1a) (wherein each X is the same and represents F or H, n5 represents 0 or an integer of 1 to 10, and A is as defined above) is a suitable example of a polymerized unit based on a fluoroallyl ether compound represented by the following formula: In the above formula (1a), 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, in that PTFE particles having a small primary particle size can be obtained, and is preferably 0, 1 or 2, and even more preferably 0 or 1. The above A is preferably -COOM in that appropriate water solubility and surface activity can be obtained, and the above M is preferably H or NH4 in that it is unlikely to remain as an impurity and the heat resistance of the obtained molded article is improved. The polymer (1) may be a homopolymer of the fluoroallyl ether compound represented by the general formula (1a) or a copolymer with other monomers.

[0051] The above polymerized units (1) are preferably polymerized units (1A) based on a monomer represented by the following general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.) The polymer (1) may be a homopolymer of the monomer represented by the general formula (1A) or a copolymer with other monomers.

[0052] Specific examples of the monomer represented by formula (1A) include those represented by the following formula:

[0053] [ka]

[0054] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is H, F or CF3; p1+q1+r1 are integers from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, except for Z 3 and Z 4 are both H, then p1+q1+r1+s1 is not 0). More specifically,

[0055] [ka]

[0056] The following are preferred, among which:

[0057] [ka]

[0058] It is preferable that:

[0059] As the monomer represented by the above general formula (1A), A in formula (1A) is preferably -COOM, and in particular, at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is as defined above) is preferred, with CH2=CFCF2OCF(CF3)COOM being more preferred.

[0060] Further, examples of the monomer represented by the general formula (1) include the monomer represented by the following formula:

[0061] CF2=CFCF2-O-Rf-A (wherein Rf and A are the same as above)

[0062] More specifically, [ka] etc.

[0063] The polymer (1) may be a homopolymer consisting of the polymerized unit (1) alone, or may be a copolymer containing the polymerized unit (1) together with a polymerized unit based on another monomer copolymerizable with the monomer represented by formula (1). From the viewpoint of solubility in the polymerization medium, a homopolymer consisting of the polymerized unit (1) alone is preferred.

[0064] The other monomer is preferably a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms, such as CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, etc. Among them, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl) and vinylidene fluoride (CH2=CF2) is preferable because of its good copolymerizability.

[0065] The other monomers include those represented by the following formula (n1-2):

[0066] [ka]

[0067] (In the formula, X 1 , X 2 are the same or different H or F;X 3 is H, F, Cl, CH3 or CF3;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. Rf 3 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having ether bonds having 2 to 100 carbon atoms).

[0068] Specifically, CH2=CFCF2-O-Rf 3 , CF2=CF-O-Rf 3 , CF2=CFCF2-O-Rf 3 , CF2=CF-Rf 3 , CH2=CH-Rf 3 , CH2=CH-O-Rf 3 (In the formula, Rf 3 is the same as the above formula (n1-2)).

[0069] As the other monomer, there may be mentioned a monomer represented by the formula (n2-1):

[0070] [ka]

[0071] (In the formula, X 9 is H, F or CH3; Rf 4 Also included are fluorine-containing acrylate monomers represented by Rf (a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond). 4 The base is

[0072] [ka]

[0073] (wherein d3 is an integer of 1 to 4; e3 is an integer of 1 to 10), etc. can be mentioned.

[0074] As the other monomer, there may be mentioned a monomer represented by the formula (n2-2): CH2=CHO-Rf 5 (n2-2) (In the formula, Rf 5 Also included are fluorine-containing vinyl ethers represented by the formula (I) (a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond).

[0075] Specific examples of the monomer of formula (n2-2) include:

[0076] [ka]

[0077] (wherein e6 is an integer of 1 to 10) are preferred.

[0078] More specifically,

[0079] [ka]

[0080] etc.

[0081] Others, formula (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (In the formula, Rf 6 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond), a fluorine-containing allyl ether represented by the formula (n2-4): CH2=CH-Rf 7 (n2-4) (In the formula, Rf 7 Also included are fluorine-containing vinyl monomers represented by the formula (I) being a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond.

[0082] Specific examples of the monomers represented by the above formulas (n2-3) and (n2-4) include:

[0083] [ka]

[0084] and the like monomers.

[0085] The content of the polymer (1) in the total polymer units is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, even more preferably 5.0 mol% or more, even more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more, and particularly preferably substantially 100 mol%. In the polymer (1), the content of polymerization units based on other monomers copolymerizable with the monomer represented by general formula (1) is preferably 70 mol % or less, more preferably 60 mol % or less, even more preferably 40 mol % or less, even more preferably 20 mol % or less, particularly preferably 10 mol % or less, and even more preferably substantially 0 mol % based on the total polymerization units.

[0086] The number average molecular weight of the polymer (1) is 0.1×10 4 More than 0.2×10 is preferable. 4 More preferably, 0.3×10 4 More preferably, 0.4×10 4 More preferably, 0.5×10 4 More preferably, 1.0×10 4 More than 3.0×10 is particularly preferable. 4 More than 75.0×10 is the most preferable. 4 Less than 50.0×10 is preferable. 4 Less than or equal to 30.0×10 is more preferable. 4 More preferably, 20.0×10 4 The following is particularly preferred. If the number average molecular weight is too low, the stability of the aqueous solution may be insufficient. If the number average molecular weight is too high, the polymer (1) may partially settle, precipitate, or become cloudy during storage or when other additives are added. The number average molecular weight and the weight average molecular weight described below are values ​​calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.

[0087] The weight average molecular weight of the polymer (1) is 0.2×10 4 More than 0.4×10 is preferable. 4 More preferably, 0.6×10 4 More preferably, 0.8×10 4 More preferably, 1.0×10 4 More than 150.0×10 4 The following is preferable: 100.0×10 4 Less than 60.0×10 is more preferable. 4More preferably, 40.0×10 4 The following are particularly preferred:

[0088] The above polymer (1) can be produced by a conventional method except for using the above monomers.

[0089] The method for producing a fluoropolymer of the present disclosure includes a step of obtaining a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing polymerized units (1) based on a monomer represented by general formula (1).

[0090] The above fluoromonomer preferably has at least one double bond. The above-mentioned fluoromonomers include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkyl ethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, and fluoroalkyl ethylene represented by the general formula (100): CH2=CFRf 101 (In the formula, Rf 101 is preferably at least one selected from the group consisting of a fluoromonomer represented by (a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluorinated vinyl heterocyclic compound, and a monomer that provides a crosslinking site.

[0091] Examples of the fluoroalkyl vinyl ether include General formula (110): CF2=CF-ORf 111 (In the formula, Rf 111 represents a perfluoro organic group; General formula (120): CF2=CF-OCH2-Rf 121 (In the formula, Rf 121 is a perfluoroalkyl group having 1 to 5 carbon atoms), General formula (130): CF2=CFOCF2ORf 131 (In the formula, Rf 131 is 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, General formula (140): CF2=CFO(CF2CF(Y 141 )O) m (CF2) n F (In the formula, Y 141 represents a fluorine atom or a trifluoromethyl group; m is an integer of 1 to 4; and n is an integer of 1 to 4. General formula (150): CF2=CF-O-(CF2CFY 151 -O) n -(CFY 152 ) m -A 151 (In the formula, Y 151 represents a fluorine atom, a chlorine atom, a -SO2F group, or a perfluoroalkyl group. The perfluoroalkyl group may contain an etheric oxygen and a -SO2F group. n represents an integer of 0 to 3. n Y 151 may be the same or different. Y 152 represents a fluorine atom, a chlorine atom, or a -SO2F group. m represents an integer of 1 to 5. m Y 152 may be the same or different. A 151 -SO2X 151 , -COZ 151 or -POZ 152 Z 153 Represents X. 151 is F, Cl, Br, I, -OR 151 or -NR 152 R 153 Represents Z. 151 , Z 152 and Z 153 are the same or different, -NR 154 R 155 -OR 156 Represents R 151, R 152 , R 153 , R 154 , R 155 and R 156 are the same or different and represent H, ammonium, an alkali metal, an alkyl group which may contain a fluorine atom, an aryl group, or a sulfonyl-containing group. It is preferable that the material is at least one selected from the group consisting of:

[0092] In this specification, the term "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoro organic group may have an ether oxygen.

[0093] The fluoromonomer represented by the general formula (110) is Rf 111 An example of a fluoromonomer is a perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

[0094] 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. The fluoromonomer represented by the general formula (110) further includes a fluoromonomer represented by the general formula (110) in which Rf 111 is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf 111 is the following formula:

[0095] [ka]

[0096] (wherein m represents 0 or an integer of 1 to 4), Rf 111 is the following formula:

[0097] [ka]

[0098] (wherein n represents an integer of 1 to 4).

[0099] Among the fluoromonomers represented by the general formula (110), General formula (160): CF2=CF-ORf 161 (In the formula, Rf 161 Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms. 161 is preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

[0100] The fluoroalkyl vinyl ether is preferably at least one selected from the group consisting of fluoromonomers represented by the general formulas (160), (130) and (140).

[0101] The fluoromonomer represented by general formula (160) 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).

[0102] The fluoromonomer represented by general formula (130) is preferably at least one selected from the group consisting of CF2=CFOCF2OCF3, CF2=CFOCF2OCF2CF3, and CF2=CFOCF2OCF2CF2OCF3.

[0103] The fluoromonomer represented by general formula (140) is preferably at least one selected from the group consisting of CF2=CFOCF2CF(CF3)O(CF2)3F, CF2=CFO(CF2CF(CF3)O)2(CF2)3F, and CF2=CFO(CF2CF(CF3)O)2(CF2)2F.

[0104] The fluoromonomer represented by general formula (150) is preferably at least one selected from the group consisting of CF2=CFOCF2CF2SO2F, CF2=CFOCF2CF(CF3)OCF2CF2SO2F, CF2=CFOCF2CF(CF2CF2SO2F)OCF2CF2SO2F and CF2=CFOCF2CF(SO2F)2.

[0105] The fluoromonomer represented by the general formula (100) is Rf 101 is a linear fluoroalkyl group, and Rf 101 More preferred is a fluoromonomer in which Rf is a straight-chain perfluoroalkyl group. 101 The number of carbon atoms is preferably 1 to 6. Examples of the fluoromonomer represented by the general formula (100) include CH2=CFCF3, CH2=CFCF2CF3, CH2=CFCF2CF2CF3, CH2=CFCF2CF2CF2H, CH2=CFCF2CF2CF2CF3, and the like, and among these, 2,3,3,3-tetrafluoropropylene represented by CH2=CFCF3 is preferred.

[0106] The fluoroalkyl ethylenes include: General formula (170): CH2=CH-(CF2) n -X 171 (In the formula, X 171 is H or F, and n is an integer of 3 to 10.) is preferred, and CH2=CH-C4F9 and CH2=CH-C6F 13 It is more preferable that the material is at least one selected from the group consisting of:

[0107] Examples of monomers that provide crosslinking sites include: General formula (180):CX 181 2=CX 182 -R f 181 CHR 181 X 183 (In the formula, X 181 and X 182 are independently a hydrogen atom, a fluorine atom, or CH3, R f 181 represents a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group; R 181 is a hydrogen atom or CH3, X 183 is an iodine atom or a bromine atom. General formula (190):CX 191 2=CX 192 -R f 191 X 193 (In the formula, X 191 and X 192 are independently a hydrogen atom, a fluorine atom, or CH3, R f 191 represents a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group; X 193 is an iodine atom or a bromine atom. General formula (200): CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 201 (In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, X 201 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CHI; and General formula (210): CH2=CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X 211 (In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, X 211is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CHOH; General formula (220):CR 221 R 222 =CR 223 -Z 221 -CR 224 =CR 225 R 226 (In the formula, R 221 , R 222 , R 223 , R 224 , R 225 and R 226 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 221 represents 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 or oxyalkylene group having 1 to 10 carbon atoms, which may have an oxygen atom, or -(Q) p -CF2O-(CF2CF2O) m (CF2O) n -CF2-(Q) p - (wherein Q is an alkylene group or an oxyalkylene group, p is 0 or 1, and m / n is 0.2 to 5), and is a (per)fluoropolyoxyalkylene group having a molecular weight of 500 to 10,000. It is preferable that the material is at least one selected from the group consisting of:

[0108] X 183 and X 193 is preferably an iodine atom. f 181 and R f 191 R is preferably a perfluoroalkylene group having 1 to 5 carbon atoms. 181 is preferably a hydrogen atom. 201 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I. 211is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CHOH.

[0109] The fluorinated vinyl heterocycle may be represented by the general formula (230): [ka] (In the formula, X 231 and X 232 are independently F, Cl, a methoxy group or a fluorinated methoxy group; Y 231 is the formula Y 232 or formula Y 233 It is.

[0110] [ka] (In the formula, Z 231 and Z 232 are independently F or a fluorinated alkyl group having 1 to 3 carbon atoms.

[0111] Monomers that provide crosslinking sites include CF2=CFOCF2CF(CF3)OCF2CF2CN, CF2=CFOCF2CF(CF3)OCF2CF2COOH, CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOH, CH2=CFCF2OCF( It is preferably at least one selected from the group consisting of CF3)CF2OCF(CF3)CH2OH, CH2=CHCF2CF2I, CH2=CH(CF2)2CH=CH2, CH2=CH(CF2)6CH=CH2, and CF2=CFO(CF2)5CN, and more preferably at least one selected from the group consisting of CF2=CFOCF2CF(CF3)OCF2CF2CN and CF2=CFOCF2CF2CH2I.

[0112] In the above step, the fluoromonomer and the fluorine-free monomer may be polymerized. The fluorine-free monomer may be a hydrocarbon monomer reactive with the fluoromonomer. Examples of the hydrocarbon monomer include alkenes such as ethylene, propylene, butylene, 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 caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, and the like. vinyl esters such as vinyl allyl ether, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, vinyl undecylenate, vinyl hydroxyacetate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, and vinyl hydroxycyclohexanecarboxylate; alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, and cyclohexyl allyl ether; and alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, and cyclohexyl allyl ester.

[0113] The above-mentioned fluorine-free monomer may also be a functional group-containing hydrocarbon monomer (excluding the monomer that provides a crosslinking site).The above-mentioned functional group-containing hydrocarbon monomer may be, for example, hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; fluorine-free monomers having carboxyl groups such as itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride, and perfluorobutenoic acid; fluorine-free monomers having glycidyl groups such as glycidyl vinyl ether and glycidyl allyl ether; fluorine-free monomers having amino groups such as aminoalkyl vinyl ether and aminoalkyl allyl ether; fluorine-free monomers having amide groups such as (meth)acrylamide and methylol acrylamide.

[0114] In the above process, one or more of the above fluoromonomers can be polymerized to obtain particles of the desired fluoropolymer.

[0115] The production method of the present disclosure can efficiently produce a fluoropolymer by using at least one of the polymers (1). In addition, in the production method of the present disclosure, two or more of the polymers (1) may be used simultaneously, and other surface-active compounds may be used simultaneously as long as they are volatile or may remain in a molded product made of a fluoropolymer.

[0116] In the production method of the present disclosure, the polymerization may be carried out in the presence of a nonionic surfactant. General formula (240): Rf 241 -(X 241 ) n -Y 241 (In the formula, Rf 241 is a partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, n is 0 or 1, and X241 is -O-, -COO- or -OCO-; Y 241 Ha-(CH2) p H, -(CH2) p OH or -(OR 241 ) q (OR 242 ) r OH, p is an integer from 1 to 12, q is an integer from 1 to 12, r is an integer from 0 to 12, and R 241 and R 242 is an alkylene group having 2 to 4 carbon atoms, where R 241 and R 242 are different from each other. General formula (250):H(OR 251 ) u (OR 252 ) v OH (In the formula, R 251 and R 252 is an alkylene group having 1 to 4 carbon atoms, and u and v are integers from 1 to 5. 251 and R 252 are different from each other.) A nonionic polymer having, in its molecule, a hydrophobic group consisting of a hydrocarbon group having 8 to 20 carbon atoms and a hydrophilic group consisting of a polyalkylene oxide, and General formula (260):R 261 m -Si-(OR 262 ) 4-m (In the formula, R 261 is an alkyl group having 1 to 12 carbon atoms; R 262 is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3, At least one selected from the group consisting of:

[0117] Specific examples of the block polymer represented by the general formula (250) include block polymers consisting of at least two types of segments selected from the group consisting of polyoxyethylene, polyoxypropylene, and polyoxybutylene. Among them, polyoxyethylene-polyoxypropylene block polymers and polyoxyethylene-polyoxybutylene block polymers are exemplified, and not only AB type but also ABA type block polymers are preferred. More preferably, by using polyoxyethylene-polyoxypropylene block polymers and polyoxypropylene-polyoxyethylene-polyoxypropylene block polymers, a highly concentrated and stable fluoropolymer dispersion can be prepared. Furthermore, when the content of the polyoxyethylene segment is 10 to 50%, it is preferable because there is little generation of aggregates thought to be due to re-aggregation, and when it is 20 to 40%, it is more preferable because a low-viscosity fluoropolymer dispersion can be prepared. The molecular weight is not particularly limited, but may be 1000 to 7000 g / mol, and more particularly when it is 2500 to 6500 g / mol, a dispersion with low viscosity and excellent dispersibility can be prepared.

[0118] In the manufacturing method of the present disclosure, a nucleating agent may be used.The preferred amount of the nucleating agent can be appropriately selected according to the type of the nucleating agent, and is, for example, 1000ppm or less, more preferably 500ppm or less, even more preferably 100ppm or less, particularly preferably 50ppm or less, and even more preferably 10ppm or less, based on the aqueous medium.

[0119] The manufacturing method of the present disclosure preferably further includes a step of adding a nucleating agent to the aqueous medium before the start of polymerization or when the concentration of polytetrafluoroethylene particles formed in the aqueous medium is 5.0 mass% or less. By adding the nucleating agent at the beginning of polymerization, an aqueous dispersion having a small average primary particle size and excellent stability can be obtained. The amount of the nucleating agent added before the start of polymerization or when the concentration of the PTFE particles formed in the aqueous medium is 5.0% by mass or less is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the polytetrafluoroethylene obtained. The upper limit is not limited, but is, for example, 2000% by mass.

[0120] The use of the nucleating agent results in a fluoropolymer having a smaller primary particle size compared to polymerization carried out in the absence of the nucleating agent.

[0121] 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.

[0122] The nucleating agent is preferably added before or simultaneously with the addition of the polymerization initiator, but by adding it during the polymerization, the particle size distribution can also be adjusted.

[0123] The amount of the dicarboxylic acid is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less, relative to the aqueous medium.

[0124] The perfluoropolyether (PFPE) acid or salt thereof may have any chain structure in which oxygen atoms in the backbone of the molecule are separated by saturated fluorocarbon groups having 1 to 3 carbon atoms. Also, two or more types of fluorocarbon groups may be present in the molecule. A representative structure has a repeat unit represented by the following formula: (-CFCF3-CF2-O-) n (VII) (-CF2-CF2-CF2-O-) n (VIII) (-CF2-CF2-O-) n-(-CF2-O-) m (IX) (-CF2-CFCF3-O-)n-(-CF2-O-) m (X)

[0125] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed therein, the PFPE acid or its salt may have a carboxylic acid group or its salt at one or both ends. The PFPE acid or its salt may also have a sulfonic acid, phosphonic acid group or their salt at one or both ends. The PFPE acid or its salt may also have a different group at each end. For monofunctional PFPEs, the other end of the molecule is usually perfluorinated, but may contain hydrogen or chlorine atoms. The PFPE acid or its salt has at least two ether oxygens, preferably at least four ether oxygens, and even more preferably at least six ether oxygens. Preferably, at least one of the fluorocarbon groups separating the ether oxygens, and more preferably at least two of such fluorocarbon groups, has two or three carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have two or three carbon atoms. Also, preferably, the PFPE acid or salt thereof has a total of at least 15 carbon atoms, for example, the preferred minimum value of n or n+m in the repeating unit structure above is at least 5. Two or more of the PFPE acids or salts thereof having an acid group at one or both termini may be used in the manufacturing method of the present disclosure. The PFPE acid or salt thereof preferably has a number average molecular weight of less than 6000 g / mol.

[0126] The amount of the hydrocarbon-containing surfactant added is preferably 40 ppm or less, more preferably 30 ppm or less, and even more preferably 20 ppm or less, relative to the aqueous medium. It is presumed that the ppm amount of lipophilic nucleation sites present in the aqueous medium is less than the amount added. Therefore, the amount of the lipophilic nucleation sites is less than the above 50 ppm, 40 ppm, 30 ppm, and 20 ppm. Since the lipophilic nucleation sites are considered to exist as molecules, even a small amount of the hydrocarbon-containing surfactant can generate a large amount of lipophilic nucleation sites. Therefore, even if the hydrocarbon-containing surfactant is added to the aqueous medium at about 1 ppm, a beneficial effect can be obtained. The preferred lower limit is 0.01 ppm, more preferably 0.1 ppm.

[0127] The hydrocarbon-containing surfactants include nonionic and cationic surfactants, including siloxane surfactants such as those disclosed in U.S. Pat. No. 7,897,682 (Brothers et al.) and U.S. Pat. No. 7,977,438 (Brothers et al.).

[0128] The hydrocarbon-containing surfactant is preferably a non-ionic surfactant (e.g., a non-ionic hydrocarbon surfactant). That is, the nucleating agent is preferably a non-ionic surfactant. The non-ionic surfactant preferably does not contain an aromatic moiety.

[0129] The nonionic surfactant may be, for example, a surfactant represented by the following general formula (i): R 3 -OA 1 -H(i) (In the formula, R 3 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms; A 1 is a polyoxyalkylene chain. R 3 R preferably has 10 to 16 carbon atoms, more preferably 12 to 16 carbon atoms. 3When the carbon number of R is 18 or less, good dispersion stability of the aqueous dispersion is easily obtained. 3 If the carbon number of R exceeds 18, the flow temperature is high and it is difficult to handle. 3 If the number of carbon atoms is less than 8, the surface tension of the aqueous dispersion becomes high, and the permeability and wettability tend to decrease.

[0130] The polyoxyalkylene chain may be composed of oxyethylene and oxypropylene. The polyoxyalkylene chain is composed of an average repeat number of oxyethylene groups of 5 to 20 and an average repeat number of oxypropylene groups of 0 to 2, and is a hydrophilic group. The number of oxyethylene units may include either a broad or narrow unimodal distribution, which is usually provided, or a broader or bimodal distribution, which is obtained by blending. When the average repeat number of oxypropylene groups is more than 0, the oxyethylene groups and oxypropylene groups in the polyoxyalkylene chain may be arranged in a block shape or a random shape. From the viewpoint of viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain having an average repeat number of 7 to 12 oxyethylene groups and an average repeat number of 0 to 2 oxypropylene groups is preferred. 1 It is preferable that the oxypropylene group has an average of 0.5 to 1.5, since this results in good low foaming properties.

[0131] More preferably, R 3 is (R')(R'')HC-, where R' and R'' are the same or different linear, branched, or cyclic alkyl groups having a total of at least 5, preferably 7 to 17 carbon atoms. Preferably, at least one of R' or R'' is a branched or cyclic hydrocarbon group.

[0132] Specific examples of the polyoxyethylene alkyl ether include C 13 H 27 -O-(C2H4O) 10 -H, C 12 H 25 -O-(C2H4O) 10 -H, C 10 H 21CH(CH3)CH2-O-(C2H4O)9-H, C 13 H 27 -O-(C2H4O)9-(CH(CH3)CH2O)-H, C 16 H 33 -O-(C2H4O) 10 -H, HC(C5H 11 )(C7H 15 )-O-(C2H4O)9-H, etc. Examples of commercially available polyoxyethylene alkyl ethers include Genapol X080 (product name, manufactured by Clariant), the Noigen TDS series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) such as Noigen TDS-80 (trade name), the Leocol TD series (manufactured by Lion Corporation) such as Leocol TD-90 (trade name), the Lionol (registered trademark) TD series (manufactured by Lion Corporation), the T-Det A series (manufactured by Harcros Chemicals) such as T-Det A138 (trade name), and the Tergitol (registered trademark) 15S series (manufactured by Dow Corporation).

[0133] The nonionic surfactant is 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. Nonionic surfactants of this type are also commercially available, for example, as TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (all product names, manufactured by Dow Chemical Company).

[0134] The hydrophobic group of the nonionic surfactant may be any one of an alkylphenol group, a linear alkyl group, and a branched alkyl group. For example, the polyoxyethylene alkylphenyl ether nonionic compound may be a compound represented by the following general formula (ii): R 4 -C6H4-OA 2 -H (ii) (In the formula, R 4is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms; A 2 is a polyoxyalkylene chain.) Specific examples of the polyoxyethylene alkylphenyl ether nonionic compounds include Triton X-100 (trade name, manufactured by Dow Chemical Co.).

[0135] The nonionic surfactant also includes a polyol compound, specifically, those described in WO 2011 / 014715. Typical examples of polyol compounds include compounds having one or more sugar units as polyol units. The sugar units may be modified to contain at least one long chain. Suitable polyol compounds containing at least one long chain moiety include, for example, alkyl glycosides, modified alkyl glycosides, sugar esters, and combinations thereof. Sugars include, but are not limited to, monosaccharides, oligosaccharides, and sorbitan. Monosaccharides include pentoses and hexoses. Typical examples of monosaccharides include ribose, glucose, galactose, mannose, fructose, arabinose, and xylose. Oligosaccharides include oligomers of 2 to 10 identical or different monosaccharides. Examples of oligosaccharides include, but are not limited to, saccharose, maltose, lactose, raffinose, and isomaltose.

[0136] Typically, suitable sugars for use as polyol compounds include cyclic compounds containing a five-membered ring with four carbon atoms and one heteroatom (typically oxygen or sulfur, but preferably an oxygen atom), or a six-membered ring with five carbon atoms and one heteroatom, preferably an oxygen atom, as described above. These further contain at least two or at least three hydroxy groups (-OH groups) attached to the carbon ring atoms. Typically, the sugars are modified in that one or more of the hydrogen atoms of the hydroxy groups (and / or hydroxyalkyl groups) attached to the carbon ring atoms are replaced by a long-chain residue, such that an ether or ester bond is created between the long-chain residue and the sugar moiety. The sugar-based polyol may contain one or more sugar units. The sugar unit or units may be modified with long chain moieties as described above. Specific examples of sugar-based polyol compounds include glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof.

[0137] A preferred class of polyol compounds are the alkyl or modified alkyl glucosides. These classes of surfactants contain at least one glucose moiety. [ka] (In the formula, x represents 0, 1, 2, 3, 4, or 5; R 1 and R 2 independently represent H or a long chain unit containing at least 6 carbon atoms, with the proviso that R 1 and R 2 At least one of R is not H. 1 and R 2Representative examples of the fatty alcohol include fatty alcohol residues. Examples of fatty alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof. The above formula represents a specific example of an alkyl polyglucoside showing glucose in the pyranose form, however, it is understood that other sugars or the same sugar but in a different enantiomeric or diastereomeric form may be used. Alkyl glucosides can be obtained, for example, by acid-catalyzed reaction of glucose, starch, or n-butyl glucoside with fatty alcohols, which typically results in a mixture of various alkyl glucosides (Alkylpolygylcoside, Rompp, Lexikon Chemie, Version 2.0, Stuttgart / New York, Georg Thieme Verlag, 1999). Examples of fatty alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof. Alkyl glucosides are also commercially available from Cognis GmbH, Dusseldorf, Germany under the trade name GLUCOPON or DISPONIL.

[0138] Other nonionic surfactants include difunctional block copolymers supplied by BASF Corporation as the Pluronic® R series, tridecyl alcohol alkoxylates supplied by BASF Corporation as the Iconol® TDA series, and hydrocarbon-containing siloxane surfactants, preferably hydrocarbon surfactants, in which the hydrocarbyl groups, which may be substituted by halogens such as fluorine, are fully substituted by hydrogen atoms, whereby these siloxane surfactants can also be considered as hydrocarbon surfactants, i.e., the monovalent substituents on the hydrocarbyl groups are hydrogen.

[0139] Furthermore, when TFE is used as the fluoromonomer to produce polytetrafluoroethylene [PTFE] as the fluoropolymer, by adding, at the start of TFE polymerization, (polyfluoroalkyl)ethylene (a) and / or comonomer (b) having a monomer reactivity ratio rTFE in copolymerization with TFE of 0.1 to 8 to the polymerization system in an amount of 0.001 to 0.01 mass % relative to the final amount of PTFE produced, the stability of the aqueous PTFE dispersion is high enough not to impair subsequent processability, moldability, etc., and an aqueous PTFE dispersion capable of producing molded products with high heat resistance can be produced.

[0140] Here, the monomer reactivity ratio in copolymerization with TFE is the value obtained by dividing the rate constant of the reaction of the growing radical with TFE by the rate constant of the reaction of the growing radical with comonomer when the growing radical is less than the repeating unit based on TFE. The lower this value, the higher the reactivity of the comonomer with TFE. The above reactivity ratio can be calculated from the composition of the polymer produced immediately after the start of copolymerization of the comonomer with TFE at various feed compositions, and the Feynman-Ross equation.

[0141] The copolymerization is carried out in a 6.0L stainless steel autoclave using 3600g of deionized degassed water, 1000ppm of ammonium perfluorooctanoate relative to the water, and 100g of paraffin wax at a pressure of 0.78MPaG and a temperature of 70°C. 0.05g, 0.1g, 0.2g, 0.5g, and 1.0g of comonomer are added to the reactor, respectively, and 0.072g of ammonium persulfate (20ppm relative to water) is added, and TFE is continuously fed to maintain the polymerization pressure of 0.78MPaG. When the amount of TFE charged reaches 100g, stirring is stopped and the reactor is depressurized until atmospheric pressure is reached. After cooling, the paraffin wax is separated to obtain an aqueous dispersion containing the produced polymer. The aqueous dispersion is stirred to coagulate the produced polymer, and then dried at 150°C. The composition of the resulting polymer is calculated by an appropriate combination of NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0142] In the manufacturing method of the present disclosure, a compound having a functional group capable of reacting by radical polymerization and a hydrophilic group may be used together with the polymer (1). Examples of the functional group capable of reacting by radical polymerization include groups having unsaturated bonds such as vinyl groups and allyl groups. Details will be described later. Examples of the hydrophilic group include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (in each formula, M represents H, NH4, or an alkali metal). Of these, -SO3M or -COOM is preferred as the hydrophilic group. Examples of the alkali metal include Na and K. Examples of the compound having a functional group capable of reacting by radical polymerization and a hydrophilic group include a compound represented by the general formula (270a): CF2=CF-(CF2) n271a -Y 271 (In the formula, n271a represents an integer of 1 to 10; Y 271 -SO3M 271 Or -COOM 271 represents M 271 represents H, NH4, or an alkali metal.), a surfactant represented by general formula (270b): CF2=CF-(CF2C(CF3)F) n271b -Y 271 (In the formula, n271b represents an integer of 1 to 5; Y 271 is the same as defined above.) A surfactant represented by general formula (270c): CF2=CF-O-(CFX 271 ) n271c -Y 271 (In the formula, X 271 represents F or CF3, n271c represents an integer of 1 to 10, Y 271 is the same as defined above.) A surfactant represented by general formula (270d): CF2=CF-O-(CF2CFX 271 O) n271d -CF2CF2-Y 271 (In the formula, n271d represents an integer of 1 to 10; Y 271 and X 271 is the same as defined above.) A surfactant represented by the general formula: (270e): CX 272 2 = CFCF2-O-(CF(CF3)CF2O) n271e -CF(CF3)-Y 271 (In the formula, each 272 are the same and represent F or H. n271e represents 0 or an integer of 1 to 10, Y 271 is as defined above.

[0143] In the production method of the present disclosure, in addition to the above-mentioned polymer (1) and other compounds having surface activity that are used as desired, additives for stabilizing each compound can be used. Examples of the additives include a buffering agent, a pH adjusting agent, a stabilizing assistant, and a dispersion stabilizer.

[0144] As the stabilizing aid, paraffin wax, fluorine-based oil, fluorine-based solvent, silicone oil, etc. are preferable. The stabilizing aid may be used alone or in combination of two or more. As the stabilizing aid, paraffin wax is more preferable. The paraffin wax may be liquid, semi-solid, or solid at room temperature, but is preferably a saturated hydrocarbon having 12 or more carbon atoms. The melting point of the paraffin wax is usually preferably 40 to 65°C, more preferably 50 to 65°C.

[0145] The amount of the stabilizing aid used is preferably 0.1 to 12 mass % based on the mass of the aqueous medium used, and more preferably 0.1 to 8 mass %. It is desirable that the stabilizing aid is sufficiently hydrophobic and completely separated from the PTFE dispersion after PTFE polymerization so as not to become a contaminating component.

[0146] In the production method of the present disclosure, polymerization is carried out by charging an aqueous medium, the polymer (1), a monomer, and other additives as necessary into a polymerization reactor, stirring the contents of the reactor, and maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of a polymerization initiator to start the polymerization reaction. After the polymerization reaction starts, monomers, polymerization initiators, chain transfer agents, the polymer (1), and the like may be additionally added depending on the purpose. The polymer (1) may be added after the polymerization reaction starts.

[0147] In the above polymerization, the polymerization temperature is usually 5 to 120° C., and the polymerization pressure is usually 0.05 to 10 MPaG. The polymerization temperature and polymerization pressure are appropriately determined depending on the type of monomer used, the molecular weight of the desired fluoropolymer, and the reaction rate.

[0148] The total amount of the polymer (1) is preferably 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferred lower limit is 0.001% by mass, and a more preferred upper limit is 1% by mass. If the amount is less than 0.0001% by mass, the dispersing power may be insufficient, and if the amount is more than 10% by mass, the effect commensurate with the amount added may not be obtained, and instead the polymerization rate may decrease or the reaction may stop. The amount of the compound added is appropriately determined depending on the type of monomer used, the molecular weight of the desired fluoropolymer, etc.

[0149] The method for producing a fluoropolymer of the present disclosure preferably further comprises a step of continuously adding the polymer (1). Continuously adding the polymer (1) means, for example, adding the polymer (1) over time, not all at once, and continuously or in portions. The polymer (1) may be added in the form of an aqueous solution containing the polymer (1) and water.

[0150] In the method for producing a fluoropolymer of the present disclosure, the step of continuously adding the polymer (1) is preferably one in which the polymer (1) is started to be added to the aqueous medium when the solid content of the fluoropolymer formed in the aqueous medium is 0.5% by mass or less. The addition of the polymer (1) is more preferably started when the solid content is 0.3% by mass or less, even more preferably when it is 0.2% by mass or less, even more preferably when it is 0.1% by mass or less, and particularly preferably started at the start of polymerization. The solid content is the concentration relative to the total of the aqueous medium and the fluoropolymer.

[0151] In the step of continuously adding the polymer (1), the amount of the polymer (1) added is preferably 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium. A preferred lower limit is 0.001% by mass, a more preferred lower limit is 0.01% by mass, and an even more preferred lower limit is 0.1% by mass. A more preferred upper limit is 1.0% by mass, and an even more preferred upper limit is 0.50% by mass. If the amount is less than 0.0001% by mass, the dispersing power may be insufficient, and if the amount exceeds 10% by mass, the effect commensurate with the amount added may not be obtained, and instead the polymerization rate may decrease or the reaction may stop. The amount of the compound added is appropriately determined depending on the type of monomer used, the molecular weight of the desired fluoropolymer, and the like.

[0152] The polymerization initiator is not particularly limited as long as it can generate radicals in the above polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, it can also be combined with a reducing agent or the like to initiate polymerization as a redox. The concentration of the polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the desired fluoropolymer, and the reaction rate.

[0153] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0154] The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, and the like. In addition, di(ω-hydro-dodecafluoroheptanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di(ω-chloro) peroxide, and the like. Representative examples of the di[perfluoro(or fluorochloro)acyl]peroxides include di(ω-hexafluorobutyryl)peroxide, di(ω-chloro-decafluorohexanoyl)peroxide, di(ω-chloro-tetradecafluorooctanoyl)peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl)peroxide, di(trichlorooctafluorohexanoyl)peroxide, di(tetrachloroundecafluorooctanoyl)peroxide, di(pentachlorotetradecafluorodecanoyl)peroxide, and di(undecachlorodotriacontafluorodocosanoyl)peroxide.

[0155] The water-soluble radical polymerization initiator may be a known water-soluble peroxide, such as ammonium salts, potassium salts, or sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, or percarbonic acid, t-butyl permaleate, or t-butyl hydroperoxide, etc. A reducing agent such as sulfites or sulfites may also be contained, and the amount used may be 0.1 to 20 times that of the peroxide.

[0156] For example, when polymerization is carried out at a low temperature of 30° C. or less, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, and cerium ammonium nitrate. Examples of the reducing agent include sulfites, bisulfites, bromates, diimines, and oxalic acid. Examples of the persulfates include ammonium persulfate and potassium persulfate. Examples of the sulfites include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the combination of the redox initiator. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate.

[0157] Examples of the redox initiator include potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / iron sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / bisulfite, and the like, with potassium permanganate / oxalic acid being preferred. When using a redox initiator, either an oxidizing agent or a reducing agent may be charged in advance into a polymerization tank, and then the other may be added continuously or intermittently to initiate polymerization. For example, when potassium permanganate / oxalic acid is used, it is preferred to charge oxalic acid into a polymerization tank and continuously add potassium permanganate thereto.

[0158] The amount of polymerization initiator to be added is not particularly limited, but may be added all at once, stepwise, or continuously in an amount (for example, several ppm relative to water concentration) at least at which the polymerization rate does not drop significantly. The upper limit is a range in which the reaction temperature may be increased while removing heat from the equipment side by the polymerization reaction heat, and a more preferable upper limit is a range in which the polymerization reaction heat can be removed from the equipment side.

[0159] The aqueous medium is a reaction medium for polymerization, and refers to a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as an alcohol, ether, or ketone, and / or a fluorine-containing organic solvent having a boiling point of 40° C. or less.

[0160] In the above polymerization, a known chain transfer agent, radical scavenger, or decomposer may be further added depending on the purpose to adjust the polymerization rate and molecular weight.

[0161] Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate, as well as isopentane, methane, ethane, propane, methanol, isopropanol, acetone, various mercaptans, various halogenated hydrocarbons such as carbon tetrachloride, and cyclohexane.

[0162] Bromine compounds or iodine compounds may be used as chain transfer agents. Examples of polymerization methods using bromine compounds or iodine compounds include a method of polymerizing a fluoromonomer in an aqueous medium in the presence of a bromine compound or iodine compound in a substantially oxygen-free state (iodine transfer polymerization method). Representative examples of the bromine compounds or iodine compounds used include, for example, compounds represented by the general formula: R a I x Br y (In the formula, x and y are each an integer of 0 to 2, and 1≦x+y≦2 is satisfied; R ais a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom). By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer and functions as a crosslinking point.

[0163] Examples of iodine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, BrCF2CFCl Br, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted benzene, and (2-iodoethyl) and (2-bromoethyl)-substituted benzene. These compounds may be used alone or in combination with each other.

[0164] Among these, it is preferable to use 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane in terms of polymerization reactivity, crosslinking reactivity, availability, and the like.

[0165] The amount of the chain transfer agent used is usually 1 to 50,000 ppm, and preferably 1 to 20,000 ppm, based on the total amount of fluoromonomers supplied.

[0166] The chain transfer agent may be added to the reaction vessel all at once before the initiation of polymerization, may be added all at once after the initiation of polymerization, may be added in several divided portions during the polymerization, or may be added continuously during the polymerization.

[0167] The production method of the present disclosure preferably further includes a step of adding a polymerization terminator (radical scavenger) (hereinafter also referred to as a "polymerization terminator addition step"). The polymerization terminator addition step is carried out during the polymerization step. The polymerization terminator is a compound that does not have the ability to restart after addition or chain transfer to the free radical in the polymerization system. Specifically, a compound that easily undergoes a chain transfer reaction with a primary radical or a growing radical, and then generates a stable radical that does not react with a monomer, or a compound that easily undergoes an addition reaction with a primary radical or a growing radical, and generates a stable radical, is used. Generally, the activity of a chain transfer agent is characterized by the chain transfer constant and the reinitiation efficiency, but among chain transfer agents, those with a reinitiation efficiency of almost 0% are called polymerization terminators. The polymerization terminator is preferably at least one selected from the group consisting of, for example, aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and cupric chloride (CuCl2). Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m- or p-salicylic acid, gallic acid, naphthol, etc. Examples of the unsubstituted phenol include o-, m- or p-nitrophenol, o-, m- or p-aminophenol, p-nitrosophenol, etc. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, naphthresorcinol, etc. Examples of aromatic amines include o-, m- or p-phenylenediamine, benzidine, and the like. Examples of the quinone compound include hydroquinone, o-, m- or p-benzoquinone, 1,4-naphthoquinone, and alizarin. Examples of thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN). Of the above polymerization terminators, quinone compounds are preferred, and hydroquinone is more preferred. From the viewpoint of reducing the standard specific gravity, the polymerization terminator is preferably added before 90% by mass of the total tetrafluoroethylene consumed in the polymerization reaction is polymerized, more preferably before 85% by mass, and even more preferably before 80% by mass of the total tetrafluoroethylene is polymerized. It is also preferable to add the fluoromonomer after 5% by mass of the total fluoromonomer consumed in the polymerization reaction has been polymerized, and it is more preferable to add the fluoromonomer after 10% by mass has been polymerized. The amount of the polymerization terminator added is preferably an amount corresponding to 0.1 to 20 ppm, and more preferably an amount corresponding to 3 to 10 ppm, of the mass of the aqueous medium used.

[0168] The manufacturing method of the present disclosure preferably further includes a step of adding a decomposer to the aqueous medium. By adding the decomposer, the radical concentration during polymerization can be adjusted. Examples of the decomposer include sulfite, bisulfite, bromate, diimine, oxalic acid, copper salt, iron salt, etc. Examples of the sulfite include sodium sulfite and ammonium sulfite. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate. The amount of the decomposer added is within a range of 25 to 300% by mass, preferably 25 to 150% by mass, and more preferably 50 to 100% by mass, based on the amount of the oxidizing agent combined as a polymerization initiator (for example, a redox initiator). It is also preferable to add the tetrafluoroethylene after 5% by mass of the total tetrafluoroethylene consumed in the polymerization reaction has been polymerized, and it is more preferable to add the tetrafluoroethylene after 10% by mass has been polymerized. The amount of the polymerization terminator added is preferably an amount corresponding to 0.1 to 20 ppm, and more preferably an amount corresponding to 3 to 10 ppm, of the mass of the aqueous medium used.

[0169] The production method of the present disclosure preferably involves polymerizing a fluoromonomer substantially in the absence of a fluorine-containing surfactant. Conventionally, a fluorine-containing surfactant has been used in the polymerization of a fluoropolymer, but the production method of the present disclosure makes it possible to obtain a fluoropolymer without using a fluorine-containing surfactant by using the above polymer (1). As used herein, "substantially in the absence of a fluorine-containing surfactant" means that the amount of the fluorine-containing surfactant is 10 ppm or less relative to the aqueous medium, preferably 1 ppm or less, more preferably 100 ppb or less, even more preferably 10 ppb or less, and even more preferably 1 ppb or less.

[0170] The above-mentioned fluorine-containing surfactant includes anionic fluorine-containing surfactants. The anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less excluding the anionic group.

[0171] The above-mentioned fluorine-containing surfactant may also be a surfactant containing fluorine in the anionic moiety having a molecular weight of 800 or less. The above-mentioned "anionic portion" refers to the portion of the above-mentioned fluorine-containing surfactant excluding the cation. For example, F(CF2) represented by the formula (I) described below n1 In the case of COOM, "F(CF2) n1 The "COO" part.

[0172] The above-mentioned fluorosurfactant also includes a fluorosurfactant having a LogPOW of 3.5 or less. The LogPOW is a partition coefficient between 1-octanol and water, and is expressed as LogP [wherein P represents the ratio of the fluorosurfactant concentration in octanol to the fluorosurfactant concentration in water when a 1:1 octanol / water mixture containing the fluorosurfactant undergoes phase separation]. The LogPOW is calculated from the HPLC elution time of the sample solution using a calibration curve of each elution time and the known octanol / water partition coefficient, which is prepared by performing HPLC on standard substances (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) having known octanol / water partition coefficients under the following conditions: column: TOSOH ODS-120T column (φ4.6 mm×250 mm, manufactured by Tosoh Corporation), eluent: acetonitrile / 0.6% by mass HClO4 water=1 / 1 (vol / vol%), flow rate: 1.0 ml / min, sample amount: 300 μL, column temperature: 40° C., and detection light: UV 210 nm.

[0173] Specific examples of the fluorine-containing surfactant include those described in U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 0142541, U.S. Patent Application Publication No. 2008 / 0015319, U.S. Patent No. 3,250,808, and the like. No. 3,271,341, JP 2003-119204 A, WO 2005 / 042593, WO 2008 / 060461, WO 2007 / 046377, WO 2007 / 119526, WO 2007 / 046482, WO 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, WO 2013 / 189824, and WO 2013 / 189826.

[0174] The anionic fluorine-containing surfactant may be a surfactant represented by the following general formula (N0 ): X n0 -Rf n0 -Y 0 (N 0 ) (In the formula, X n0 is H, Cl or F. n0 Y is a linear, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H's are substituted with F, and the alkylene group may contain one or more ether bonds, and some of the H's may be substituted with Cl. 0 is an anionic group. Y 0 The anionic group may be -COOM, -SO2M, or -SO3M, and may be -COOM or -SO3M. M is H, a metal atom, or NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group. The metal atom includes alkali metals (Group 1), alkaline earth metals (Group 2), etc., such as Na, K, or Li. R 7 As the 1-10 may be an organic group of H or C 1-4 may be an organic group of H or C 1-4 The alkyl group may be: M is H, a metal atom or NR 7 4, H, an alkali metal (group 1), an alkaline earth metal (group 2) or NR 7 4, which may be H, Na, K, Li or NH4. Above Rf n0 may be one in which 50% or more of H is substituted with fluorine.

[0175] The above general formula (N 0 ) is represented by the following: The following general formula (N 1 ): Xn0 -(CF2) m1 -Y 0 (N 1 ) (In the formula, X n0 is H, Cl, or F; m1 is an integer of 3 to 15; Y 0 is as defined above, a compound represented by the following general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 ) (In the formula, Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, and X n1 is F or CF3, and Y 0 is as defined above, a compound represented by the following general formula (N 3 ): Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 ) (In the formula, Rf n2 is a partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y 0 is as defined above, a compound represented by the following general formula (N 4 ): Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 ) (In the formula, 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; Y n1 and Y n2are the same or different and are H or F, p is 0 or 1, and Y 0 is as defined above.) and a compound represented by the following general formula (N 5 ): [ka] (In the formula, X n2 , X n3 and X n4 Rf may be the same or different and are H, F, or a linear or branched partially or completely 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, which may contain an ether bond; L is a linking group; Y 0 is as defined above, where X n2 , X n3 , X n4 and Rf n5 The total number of carbon atoms is 18 or less.

[0176] The above general formula (N 0 More specifically, the compound represented by the formula (I) is a perfluorocarboxylic acid (I), a ω-H perfluorocarboxylic acid (II), a perfluoropolyether carboxylic acid (III), a perfluoroalkyl alkylene carboxylic acid (IV), a perfluoroalkoxy fluorocarboxylic acid (V), a perfluoroalkyl sulfonic acid (VI), a ω-H perfluoro sulfonic acid (VII), a perfluoroalkyl alkylene sulfonic acid (VIII), a perfluoroalkyl alkylene sulfonic acid (VIII), a perfluoroalkyl alkylene carboxylic acid (IX), a fluorocarboxylic acid (X), a fluorocarboxylic acid (X), a alkoxy fluoro sulfonic acid (XI), and a compound (XII) represented by the formula (XII).

[0177] The perfluorocarboxylic acid (I) is represented by the following general formula (I): F(CF2) n1 COOM (I) (In the formula, n1 is an integer of 3 to 14, and M is H, a metal atom, or NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group.

[0178] The ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II): H(CF2) n2 COOM (II) (wherein n2 is an integer of 4 to 15, and M is as defined above).

[0179] The perfluoropolyether carboxylic acid (III) is represented by the following general formula (III): Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III) (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.

[0180] The perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV): Rf 2 (CH2) n4 Rf 3 COOM (IV) (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, and Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above.

[0181] The alkoxyfluorocarboxylic acid (V) is represented by the following general formula (V): Rf 4 -O-CY 1 Y 2 CF2-COOM (V) (In the formula, 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; Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.

[0182] The perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI): F(CF2) n5 SO3M (VI) (wherein n5 is an integer of 3 to 14, and M is as defined above).

[0183] The above ω-H perfluorosulfonic acid (VII) is represented by the following general formula (VII): H(CF2) n6 SO3M (VII) (wherein n6 is an integer of 4 to 14, and M is as defined above).

[0184] The perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII): Rf 5 (CH2) n7 SO3M (VIII) (In the formula, Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.

[0185] The alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX): Rf 6 (CH2) n8 COOM (IX) (In the formula, Rf 6is 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 from 1 to 3, and M is as defined above.

[0186] The fluorocarboxylic acid (X) is represented by the following general formula (X): Rf 7 -O-Rf 8 -O-CF2-COOM (X) (In the formula, Rf 7 is a linear or branched, partially or completely fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether bond; Rf 8 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above.

[0187] The alkoxyfluorosulfonic acid (XI) is represented by the following general formula (XI): Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI) (In the formula, Rf 9 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, and which is partially or completely fluorinated; Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.

[0188] The compound (XII) is represented by the following general formula (XII): [ka] In the formula, X 1 , X 2 and X 3 Rf may be the same or different and are H, F and linear or branched partially or completely fluorinated alkyl groups having 1 to 6 carbon atoms, which may contain ether bonds; 10is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 is an anionic group. Y 0 may be -COOM, -SO2M, or -SO3M, or may be -SO3M or COOM, where M is as defined above. Examples of L include a single bond and a partially or completely fluorinated alkylene group having 1 to 10 carbon atoms which may contain an ether bond.

[0189] As described above, examples of the anionic fluorine-containing surfactant include carboxylic acid surfactants and sulfonic acid surfactants.

[0190] The method for producing the fluoropolymer may comprise the steps of: (I) polymerizing the fluoromonomer in an aqueous medium in the presence of the polymer (1) to produce an aqueous dispersion of fluoropolymer (A) particles; and (II) seed-polymerizing the fluoromonomer onto the fluoropolymer (A) particles in the aqueous dispersion of the fluoropolymer (A) particles.

[0191] The fluoropolymer preferably produced by the production method of the present disclosure may be any fluoropolymer different from the above polymer (1), and examples thereof include a TFE polymer in which the monomer having the largest molar fraction in the polymer (hereinafter, the "most abundant monomer") is TFE, a VDF polymer in which the most abundant monomer is VDF, and a CTFE polymer in which the most abundant monomer is CTFE.

[0192] The TFE polymer may suitably be a TFE homopolymer or a copolymer consisting of (1) TFE, (2) one or more fluorine-containing monomers other than TFE having 2 to 8 carbon atoms, particularly VDF, HFP or CTFE, and (3) other monomers. Examples of the (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-hydroperfluoroolefin, etc.

[0193] The TFE polymer may also be a copolymer of TFE and one or more fluorine-free monomers. Examples of the fluorine-free monomers include alkenes such as ethylene and propylene; vinyl esters; and vinyl ethers. The TFE polymer may also be a copolymer of TFE and one or more fluorine-containing monomers having 2 to 8 carbon atoms and one or more fluorine-free monomers.

[0194] The VDF polymer may suitably be a VDF homopolymer [PVDF] or a copolymer of (1) VDF, (2) one or more fluoroolefins other than VDF having 2 to 8 carbon atoms, particularly TFE, HFP or CTFE, and (3) a perfluoro(alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms.

[0195] The CTFE polymer may suitably be a CTFE homopolymer or a copolymer 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.

[0196] The CTFE polymer may also be a copolymer of CTFE and one or more non-fluorine-containing monomers, such as alkenes such as ethylene and propylene; vinyl esters; and vinyl ethers.

[0197] The fluoropolymers produced by the process of the present disclosure may be glassy, ​​plastic or elastomeric. They may be amorphous or partially crystalline and may be subject to compression sintering, melt processing or non-melt processing.

[0198] In the production method of the present disclosure, for example, (I) as a non-melt-processable fluororesin, tetrafluoroethylene polymer [TFE polymer (PTFE)], (II) as a melt-processable fluororesin, ethylene / TFE copolymer [ETFE], TFE / HFP copolymer [FEP], TFE / perfluoro(alkyl vinyl ether) copolymer [PFA, MFA, etc.], TFE / VDF copolymer, electrolyte polymer precursor, (III) as a fluororubber, TFE / propylene copolymer, TFE / propylene / third monomer copolymer (the third monomer is VDF, HFP, CTFE, fluoroalkyl vinyl ethers, etc.), copolymers consisting of TFE and fluoroalkyl vinyl ethers; HFP / ethylene copolymer, HFP / ethylene / TFE copolymer; PVDF; thermoplastic elastomers such as VDF / HFP copolymer, HFP / ethylene copolymer, VDF / TFE / HFP copolymer; and fluorine-containing segmented polymers described in JP-B-61-49327 can be suitably produced.

[0199] The fluoropolymer is preferably a fluororesin, and among these, a fluororesin having a fluorine substitution rate of 50% or more, as calculated by the following formula, is more preferable, a fluororesin having a fluorine substitution rate of more than 50% is even more preferable, a fluororesin having a fluorine substitution rate of 55% or more is even more preferable, a fluororesin having a fluorine substitution rate of 60% or more is even more preferable, a fluororesin having a fluorine substitution rate of 75% or more is even more preferable, a fluororesin having a fluorine substitution rate of 80% or more is particularly preferable, and a fluororesin having a fluorine substitution rate of 90 to 100%, i.e., a perfluororesin, is most preferable. (formula) Fluorine substitution rate (%) = (number of fluorine atoms bonded to carbon atoms constituting the fluoropolymer) / ((number of hydrogen atoms bonded to carbon atoms constituting the fluoropolymer) + (number of fluorine atoms and chlorine atoms bonded to carbon atoms constituting the fluoropolymer)) x 100

[0200] As the perfluororesin, a fluororesin having a fluorine substitution rate of 95 to 100% is more preferable, PTFE, FEP, and PFA are further preferable, and PTFE is particularly preferable.

[0201] The above-mentioned (I) non-melt-processable fluororesin, (II) melt-processable fluororesin, and (III) fluororubber, which are suitably produced by the production method of the present disclosure, are preferably produced in the following manner.

[0202] (I) Non-melt processable fluororesin In the production method of the present disclosure, polymerization of TFE is usually carried out at a polymerization temperature of 10 to 150°C and a polymerization pressure of 0.05 to 5 MPaG. For example, the polymerization temperature is more preferably 30°C or higher, and even more preferably 50°C or higher. Also, it is more preferably 120°C or lower, and even more preferably 100°C or lower. Also, the polymerization pressure is more preferably 0.3 MPaG or higher, and even more preferably 0.5 MPaG or higher, and even more preferably 5.0 MPaG or lower, and even more preferably 3.0 MPaG or lower. In particular, from the viewpoint of improving the yield of the fluoropolymer, it is preferably 1.0 MPaG or higher, more preferably 1.2 MPaG or higher, even more preferably 1.5 MPaG or higher, and even more preferably 2.0 MPaG or higher.

[0203] In one embodiment, the polymerization is carried out by charging pure water into a pressure-resistant reaction vessel equipped with a stirrer, deoxidizing, charging TFE, adjusting the temperature to a predetermined temperature, and adding a polymerization initiator to start the reaction. If 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 has been supplied, the supply is stopped, the TFE in the reaction vessel is purged, and the temperature is returned to room temperature to terminate the reaction. Additional TFE may be continuously or intermittently supplied to prevent the pressure from decreasing.

[0204] In the production of the TFE polymer (PTFE), various known modified monomers can also be used in combination. In this specification, the TFE polymer is a concept that includes not only TFE homopolymers, but also copolymers of TFE and modified monomers that are not melt-processable (hereinafter referred to as "modified PTFE").

[0205] Examples of the modified monomer include perhaloolefins such as HFP, CTFE, and perfluorovinyl ether; fluoro(alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms; cyclic fluorinated monomers such as fluorodioxole; perhaloalkylethylenes such as (perfluoroalkyl)ethylene; ω-hydroperhaloolefins, etc. The modified monomer can be added all at once at the beginning, or added in continuous or intermittent divided portions depending on the purpose and the supply of TFE.

[0206] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (A): CF2=CF-ORf (A) (wherein Rf represents a perfluoro organic group). In this specification, the "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoro organic group may have an ether oxygen.

[0207] An example of the perfluorovinyl ether is perfluoro(alkyl vinyl ether) [PAVE], where Rf in the general formula (A) is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0208] Examples of the perfluoroalkyl group in the PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0209] The perfluorovinyl ether further includes those in which Rf in the above general formula (A) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and those in which Rf is the following formula:

[0210] [ka]

[0211] (wherein m represents 0 or an integer of 1 to 4), Rf is a group represented by the following formula:

[0212] [ka]

[0213] (wherein n represents an integer of 1 to 4).

[0214] The (perfluoroalkyl)ethylene (PFAE) is not particularly limited, and examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.

[0215] A preferred example of the modifying monomer is the comonomer (3) having a monomer reactivity ratio of 0.1 to 8. The presence of the comonomer (3) makes it possible to obtain modified PTFE particles having a small particle size, and to obtain an aqueous dispersion having high dispersion stability.

[0216] Here, the monomer reactivity ratio in copolymerization with TFE is the value obtained by dividing the rate constant of the reaction of the growing radical with TFE by the rate constant of the reaction of the growing radical with comonomer when the growing radical is less than the repeating unit based on TFE. The lower this value, the higher the reactivity of the comonomer with TFE. The monomer reactivity ratio can be calculated by the composition in the polymer produced immediately after the start of copolymerization of TFE with comonomer and using the Feynman-Ross equation. The copolymerization is carried out in a 6.0L stainless steel autoclave using 3600g of deionized degassed water, 1000ppm of ammonium perfluorooctanoate relative to the water, and 100g of paraffin wax at a pressure of 0.78MPaG and a temperature of 70°C. 0.05g, 0.1g, 0.2g, 0.5g, and 1.0g of comonomer are added to the reactor, respectively, and 0.072g of ammonium persulfate (20ppm relative to water) is added, and TFE is continuously fed to maintain the polymerization pressure of 0.78MPaG. When the amount of TFE charged reaches 1000g, stirring is stopped and the reactor is depressurized until atmospheric pressure is reached. After cooling, the paraffin wax is separated to obtain an aqueous dispersion containing the produced polymer. The aqueous dispersion is stirred to coagulate the produced polymer, and then dried at 150°C. The composition of the resulting polymer is calculated by an appropriate combination of NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0217] The comonomer (3) having a monomer reactivity ratio of 0.1 to 8 is preferably at least one selected from the group consisting of comonomers represented by formulas (3a) to (3d). CH2=CH-Rf 1 (3a) (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms. CF2=CF-O-Rf 2 (3b) (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 2 carbon atoms. CF2=CF-O-(CF2) n CF=CF2(3c) (In the formula, n is 1 or 2.)

[0218] [ka] (In the formula, X 3 and X 4 is F, Cl or a methoxy group, and Y is of formula Y1 or Y2.

[0219] [ka] (In formula Y2, Z and Z' are F or a fluorinated alkyl group having 1 to 3 carbon atoms.)

[0220] The content of the comonomer (3) is preferably in the range of 0.00001 to 1.0% by mass based on the modified PTFE. The lower limit is more preferably 0.0001% by mass, further preferably 0.001% by mass, further more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is more preferably 0.50% by mass, further preferably 0.40% by mass, further more preferably 0.30% by mass, particularly preferably 0.10% by mass, and particularly preferably 0.05% by mass.

[0221] The modified monomer is preferably at least one selected from the group consisting of hexafluoropropylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and modified monomers having a functional group capable of reacting by radical polymerization and a hydrophilic group, since it is possible to obtain an aqueous dispersion having a small average primary particle diameter of polytetrafluoroethylene particles, a small aspect ratio, and excellent stability.

[0222] 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. 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. The total amount of the hexafluoropropylene unit, the perfluoro(alkyl vinyl ether) unit and the (perfluoroalkyl)ethylene unit is preferably in the range of 0.00001 to 1.0% by mass based on the modified PTFE. The lower limit of the total amount is more preferably 0.001% by mass, further preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is more preferably 0.50% by mass, further preferably 0.40% by mass, further more preferably 0.30% by mass, particularly preferably 0.10% by mass, and particularly preferably 0.05% by mass.

[0223] In the manufacturing method of the present disclosure, a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group (hereinafter referred to as "modified monomer (A)") may be used together with the surfactant. The modified monomer (A) may be any compound having surface activity and containing at least one vinyl group. Examples of the hydrophilic group in the modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (in each formula, M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. Of these, -SO3M or -COOM is preferred as the hydrophilic group. R 7 As the 1-10 is preferably an organic group represented by the formula: 1-4 More preferred is an organic group represented by the formula: 1-4 More preferred are alkyl groups of the formula: The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (group 1) or an alkaline earth metal (group 2), with Na, K or Li being preferred. Examples of the "functional group capable of reacting by radical polymerization" in the modified monomer (A) include: Examples of the group having an ethylenically unsaturated bond include the group Ra Preferred examples of the linking group include groups having an unsaturated bond such as -CH=CH2, -CF=CH2, -CH=CF2, -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CF=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, and -O-CF2-CF=CF2. The modifying monomer (A) is represented by the general formula (4): CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4) (In the formula, X i , X j and X k are each independently F, Cl, H, or CF; Y 3 is a hydrophilic group; R a is a linking group; Z 1 and Z 2 are each independently H, F or CF3; and k is 0 or 1). Examples of the hydrophilic group include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (in each formula, M is H, a metal atom, or NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. Of these, -SO3M or -COOM is preferred as the hydrophilic group. R 7 As the 1-10 is preferably an organic group represented by the formula: 1-4More preferred is an organic group represented by the formula: 1-4 More preferred are alkyl groups of the formula: The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (group 1) or an alkaline earth metal (group 2), with Na, K or Li being preferred. By using the modifying monomer (A), it is possible to obtain an aqueous dispersion having a smaller average primary particle size and excellent stability, and also to reduce the aspect ratio of the primary particles.

[0224] Above R a is a linking group. In this specification, the term "linking group" refers to a divalent linking group. The linking group may be a single bond, and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. There is no upper limit, but it may be, for example, 100 or less, or 50 or less. The linking group may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and may optionally contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may optionally contain one or more functional groups selected from the group consisting of esters, amides, sulfonamides, carbonyls, carbonates, urethanes, ureas, and carbamates. The linking group may not contain carbon atoms, but may be a catenary heteroatom such as oxygen, sulfur, or nitrogen.

[0225] Above R a is preferably, for example, a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group. R a When R is a divalent organic group, the hydrogen atom bonded to the carbon atom may be replaced with a halogen atom other than fluorine, such as chlorine, and may or may not contain a double bond. a may be either linear or branched, and may be either cyclic or noncyclic. a may contain functional groups (eg, esters, ethers, ketones, amines, halides, etc.). R a may also be a non-fluorinated divalent organic group, or a partially fluorinated or perfluorinated divalent organic group. R a Examples of the hydrocarbon group include a hydrocarbon group having no fluorine atoms bonded to a carbon atom, a hydrocarbon group in which some of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms, a hydrocarbon group in which all of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms, -(C=O)-, -(C=O)-O-, or a hydrocarbon group containing -(C=O)-, which may contain an oxygen atom, a double bond, or a functional group.

[0226] R a is preferably -(C=O)-, -(C=O)-O-, or a hydrocarbon group having 1 to 100 carbon atoms which may contain an ether bond and may contain a carbonyl group, and in the hydrocarbon group, some or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine. R a Preferably, -(CH2) a -, -(CF2) a -, -O-(CF2) a -, -(CF2) a -O-(CF2) b -, -O(CF2) a -O-(CF2) b -, -(CF2) a -[O-(CF2) b ] c -, -O(CF2) a -[O-(CF2) b ] c -,-[(CF2) a -O] b -[(CF2) c -O] d -, -O[(CF2) a -O] b -[(CF2) c -O] d -, -O-[CF2CF(CF3)O] a -(CF2) b-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2) a -, -(C=O)-(CF2) a -, -(C=O)-O-(CH2) a -, -(C=O)-O-(CF2) a -, -(C=O)-[(CH2) a -O] b -, -(C=O)-[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -, -(C=O)-O[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -(CH2) c -, -(C=O)-O[(CF2) a -O] b -(CF2) c -, -(C=O)-(CH2) a -O-(CH2) b -, -(C=O)-(CF2) a -O-(CF2) b -, -(C=O)-O-(CH2) a -O-(CH2) b -, -(C=O)-O-(CF2) a -O-(CF2) b At least one selected from the group consisting of -, -(C=O)-O-C6H4-, and combinations thereof. In the formula, a, b, c, and d are independently at least 1. a, b, c, and d may be independently 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.

[0227] R aSpecific examples suitable as -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3) CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CH2-, -(C=O)-, -(C=O)-O-, -(C=O)- (CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -, -(C=O)-[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-(CH2)2-O-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-, -(C=O)-O-(CF2)2-O-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-, -(C=O)-O-C6H4- and the like. a Specifically, -CF2-O-, -CF2-O-CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2 -O-CF(CF3)CF2-O-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-O-(CH2)-, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CH2)2-O] n Preferred are -(CH2)-, -(C=O)-(CH2)2-O-(CH2)-, or -(C=O)-O-C6H4-. In the above formula, n is an integer of 1-10.

[0228] -R in the above general formula (4) a -(CZ 1 Z2 ) k としては、-CF2-O-CF2-、-CF2-O-CF(CF3)-、-CF2-OC(CF3)2-、-CF2-O-CF2-CF2-、-CF2-O-CF2-CF(CF3)-、-CF2-O-CF2-C(CF3)2-、-CF2-O-CF2CF2-CF2-、-CF2-O-CF2CF2-CF (CF3)-、-CF2-O-CF2CF2-C(CF3)2-、-CF2-O-CF(CF3)-CF2-、-CF2-O-CF(CF3)-CF(CF 3)-、-CF2-O-CF(CF3)-C(CF3)2-、-CF2-O-CF(CF3)-CF2-、-CF2-O-CF(CF3)-CF(CF3) -、-CF2-O-CF(CF3)-C(CF3)2-、-CF2-O-CF(CF3)CF2-CF2-、-CF2-O-CF(CF3)CF2-CF( CF3)-、-CF2-O-CF(CF3)CF2-C(CF3)2-、-CF2-O-CF(CF3)CF2-O-CF2-、-CF2-O-CF(CF 3)CF2-O-CF(CF3)-、-CF2-O-CF(CF3)CF2-OC(CF3)2-、-(C=O)-、-(C=O)-O-、-(C=O)- (CH2)-、-(C=O)-(CF2)-、-(C=O)-O-(CH2)-、-(C=O)-O-(CF2)-、-(C=O)-[(CH2)2-O] n -(CH2)-、-(C=O)-[(CF2)2-O] n -(CF2)-、-(C=O)-[(CH2)2-O] n -(CH2)-(CH2)-、-(C=O)-[(CF2)2-O] n -(CF2)-(CF2)-、-(C=O)-O[(CH2)2-O] n -(CF2)-、-(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-、-(C=O)-O[(CF2)2-O] n -(CF2)-、-(C=O)-O[(CF2)2-O] n-(CF2)-(CF2)-, -(C=O)-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-(CH2)-, -(C=O )-O-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, -(C=O)-O-(CF2)2-O-(CF2)-C(CF3)2-, or -(C=O)-O-C6H4- C(CF3)2- is preferred, -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(C F3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -(C=O)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CH2)-(CH2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2- or -(C=O)-O-C6H4-C(CF3)2- are more preferred. In the above formula, n is an integer of 1-10.

[0229] Specific examples of the compound represented by formula (4) include: [ka] (In the formula, X j and Y 3 is the same as above. n is an integer of 1 to 10.

[0230] R a The following general formula (r1): -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g - (r1) (In the formula, X 6are each independently H, F or CF3, 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 is preferably a divalent group represented by the following general formula (r2): -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g - (r2) (In the formula, X 7 are each independently H, F or CF3, e is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1.) is also preferred.

[0231] -R in the above general formula (4) a -CZ 1 Z 2 - may also be represented by the following formula (t1): -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 - (t1) (In the formula, X 6 are each independently H, F, or CF3, 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, i is 0 or 1, and Z 1 and Z 2 are each independently F or CF3), and in formula (t1), Z 1 and Z 2 More preferably, one is F and the other is CF3. In addition, in the above general formula (4), -R a -CZ 1 Z 2 - is represented by the following formula (t2): -(C=O) h -(O) i -CF2-O-(CX 7 2)e -(O) g -CZ 1 Z 2 - (t2) (In the formula, X 7 are each independently H, F, or CF3, e is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, and Z 1 and Z 2 are each independently H, F or CF3), and in the formula (t2), Z 1 and Z 2 More preferably, one is F and the other is CF3.

[0232] The compound represented by the general formula (4) is a hydrophilic group (Y 3 ), it is also preferable that the compound has a C-F bond and does not have a C-H bond. That is, in the general formula (4), X i , X j , and X k All of the are F and R a is preferably a perfluoroalkylene group having 1 or more carbon atoms, and the perfluoroalkylene group may be either linear or branched, may be either cyclic or noncyclic, and may contain at least one catenary heteroatom. The number of carbon atoms in the perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0233] The compound represented by the general formula (4) may be partially fluorinated. That is, the compound represented by the general formula (4) may have a hydrophilic group (Y 3 ), it is also preferred that the alkyl group has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0234] The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4a): CF2=CF-O-Rf 0 -Y 3 (4a) (In the formula, Y 3 is a hydrophilic group, and Rf 0is a perfluorinated divalent linking group which may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and which optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0235] The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4b). CH2=CH-O-Rf 0 -Y 3 (4b) (In the formula, Y 3 is a hydrophilic group, and Rf 0 is a perfluorinated divalent linking group defined by formula (4a).

[0236] In the general formula (4), Y 3 In one preferred embodiment, Y is -OSO3M. 3 is -OSO3M, examples of the polymerized units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2CH2OSO3M)]-, -[CH2CH((CF2)4CH2OSO3M)]-, -[CF2CF(O(CF2)4CH2OSO3M)]-, -[CF2CF(OCF2CF(CF3)CH2OSO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CH 2OSO3M)]-, -[CH2CH((CF2)4CH2OSO3M)]-, -[CF2CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M)]-, -[CH2CH(CF2CF2CH2OSO3M)]-, -[CF2CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M)]-, -[CH2CH(CF2CF2CH2OSO3M)]-, etc. In the above formula, M is the same as above.

[0237] In the general formula (4), Y 3 Another preferred form is -SO3M. 3When is -SO3M, examples of the polymerized unit based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2SO3M)]-, -[CF2CF(O(CF2)4SO3M)]-, -[CF2CF(OCF2CF(CF3)SO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M)]-, -[CH2CH((CF2)4SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, -[CH2CH((CF2)4SO3M)]-, etc. In the above formula, M is the same as above.

[0238] In the general formula (4), Y 3 It is also a preferred form for Y to be -COOM. 3 is -COOM, the polymerized units based on the compound represented by the general formula (4) include -[CF2CF(OCF2CF2COOM)]-, -[CF2CF(O(CF2)5COOM)]-, -[CF2CF(OCF2CF(CF3)COOM)]-, -[CF2CF(OCF2CF(CF3)O(CF2) n COOM)]-(n is greater than 1), -[CH2CH(CF2CF2COOM)]-, -[CH2CH((CF2)4COOM)]-, -[CH2CH(CF2CF2COOM)]-, -[CH2CH((CF2)4COOM)]-, -[CF2CF(OCF2CF2SO2NR'CH2COOM)]-, -[CF2CF(O(CF2)4SO2NR'CH2COOM)]-, -[CF2CF(OCF2CF(CF3)SO2NR'CH2COOM)]-, -[CF2CF( OCF2CF(CF3)OCF2CF2SO2NR'CH2COOM)]-, -[CH2CH(CF2CF2SO2NR'CH2COOM)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CF2CF2CF2SO2NR'CH2COOM)]-, -[CH2CH((CF2)4SO2NR'CH2COOM)]-, -[CH2CH(CF2CF2SO2NR'CH2COOM)]-, -[CH2CH((CF2)4SO2NR'CH2COOM)]-, and the like. In the above formula, R' is H or C1-4 is an alkyl group, and M is the same as above.

[0239] In the general formula (4), Y 3 In another preferred embodiment, Y is -OPO3M. 3 is -OPO3M, examples of the polymerization units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2CH2OP(O)(OM)2)]-, -[CF2CF(O(CF2)4CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF2SO2N(C H3)CH2CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2)]-, -[CH2CH(CF2CF2CH2OP(O)(OM)2)]-, -[CH2CH((CF2)4CH2OP(O)(OM)2)]-, -[CH2CH(CF2CF2CH2OP(O)(OM)2)]-, -[CH2CH((CF2)4CH2OP(O)(OM)2)]-, and the like. In the above formula, M is the same as above.

[0240] In the general formula (4), Y 3 In another preferred embodiment, Y is -PO3M. 3 is -PO3M, examples of the polymerized units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2P(O)(OM)2)]-, -[CF2CF(O(CF2)4P(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)P(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2)]-, -[CH2CH(CF2CF2P(O)(OM)2)]-, -[CH2CH((CF2)4P(O)(OM)2)]-, -[CH2CH(CF2CF2P(O)(OM)2)]-, and -[CH2CH((CF2)4P(O)(OM)2)]-, in which M is the same as above.

[0241] The compound represented by the above general formula (4) is represented by the following general formula (5): CX2=CY(-CZ2-O-Rf-Y 3 ) (5) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluorine-containing alkyl group. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. Y 3 is the same as above.) A monomer represented by the following general formula (6): CX2=CY(-O-Rf-Y 3 ) (6) (In the formula, X is the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. Y 3 is the same as above.) and a monomer represented by the following general formula (7): CX2=CY(-Rf-Y 3 ) (7) (In the formula, X is the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. Y 3 is the same as above.

[0242] In the above general formula (5), X is -H or -F. Both X's may be -H, both X's may be -F, or at least one X may be -H. For example, one X may be -F and the other X may be -H, or both X's may be -H.

[0243] In the above general formula (5), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group containing no fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has a carbon number of at most 6, more preferably at most 4, and even more preferably at most 3. The above-mentioned fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the carbon number may be at least 1. The above-mentioned fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less carbon atoms. The above Y is preferably -H, -F or -CF3, and more preferably -F.

[0244] In the above general formula (5), Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. The alkyl group is an alkyl group containing no fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has a carbon number of at most 6, more preferably at most 4, and even more preferably at most 3. The above-mentioned fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the carbon number may be at least 1. The above-mentioned fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less carbon atoms. The above Z is preferably -H, -F or -CF3, and more preferably -F.

[0245] In the above general formula (5), it is preferable that 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.

[0246] In the above general formula (5), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not include a structure in which an oxygen atom is at the terminal, and contains an ether bond between carbon atoms. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. Also, the number is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0247] The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more, and more preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less. For example, the following formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is H, F or CF3; p1+q1+r1 are integers from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, except for Z 3 and Z 4 When both are H, p1+q1+r1+s1 is not 0). Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)- (wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF(CF3)CH2- and the like. The above-mentioned fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0248] In the above general formula (5), Y 3 is -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 are H or an organic group and may be the same or different. Any two of them may be bonded to each other to form a ring. R 7 As the 1-10 is preferably an organic group represented by the formula: 1-4 More preferred is an organic group represented by the formula: 1-4 More preferred are alkyl groups of the formula: The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li. The above M is -H, a metal atom, or -NR 7 4 is preferred, and -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7 4 is more preferred, -H, -Na, -K, -Li or -NH4 is even more preferred, -Na, -K or -NH4 is even more preferred, -Na or -NH4 is especially preferred, and -NH4 is most preferred. Above Y 3 As the alkyl group, -COOM or -SO3M is preferable, and -COOM is more preferable.

[0249] The monomer represented by the general formula (5) may be, for example, a monomer represented by the following formula (5a): CX h 2 = CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5a) (In the formula, each h are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, Y 3 is the same as defined above.) is a suitable example of a fluoroallyl ether compound. In the general formula (5a), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in that PTFE particles having a small primary particle size can be obtained. 3 is preferably -COOM in that it provides suitable water solubility and surface activity, and the above M is preferably H or NH4 in that it is less likely to remain as an impurity and improves the heat resistance of the resulting composition and the drawn body obtained from the composition.

[0250] The monomer represented by the general formula (5) is preferably a monomer (5b) represented by the following general formula (5b). CH2=CF(-CF2-O-Rf-Y 3 ) (5b) (Wherein, Rf and Y 3 is the same as above.)

[0251] Specific examples of the monomer represented by the general formula (5b) include those represented by the following formula:

[0252] [ka]

[0253] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is H, F or CF3; p1+q1+r1 are integers between 0 and 10; s1 is 0 or 1; t1 is an integer between 0 and 5; Y 3 is the same as above, except for Z 3 and Z 4 are both H, then p1+q1+r1+s1 is not 0). More specifically,

[0254] [ka]

[0255] The following are preferred, among which:

[0256] [ka]

[0257] It is preferable that:

[0258] The monomer represented by the above general formula (5b) is, for example, Y 3 is preferably -COOM, and particularly preferably at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is as defined above), and more preferably CH2=CFCF2OCF(CF3)COOM.

[0259] The monomer represented by the general formula (5) is preferably a monomer (5c) represented by the following general formula (5c). CX 2 2 = CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5c) (In the formula, each 2 are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, Y 3 is the same as the above definition.)

[0260] In the above formula (5c), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in terms of the stability of the resulting aqueous dispersion. 3 -COOM is advantageous in that it provides moderate water solubility and stability of aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the obtained molded article is improved.

[0261] The perfluorovinyl alkyl compound represented by the above formula (5c) is, for example, CH2=CFCF2OCF(CF3)COOM 1, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM 1 (In the formula, M 1 is the same as above.)

[0262] Further, examples of the monomer represented by the general formula (5) include a monomer represented by the following general formula (5d) and a monomer represented by the following general formula (5e).

[0263] CF2=CFCF2-O-Rf-Y 3 (5d) CF2=CF-Rf-Y 3 (5e) (Wherein, Rf and Y 3 is the same as above)

[0264] More specifically, [ka] etc.

[0265] In the above general formula (6), X is -H or -F. Both X's may be -F, or at least one X may be -H. For example, one X may be -F and the other may be -H, or both X's may be -H.

[0266] In the above general formula (6), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group containing no fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has a carbon number of at most 6, more preferably at most 4, and even more preferably at most 3. The above-mentioned fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the carbon number may be at least 1. The above-mentioned fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less carbon atoms. The above Y is preferably -H, -F or -CF3, and more preferably -F.

[0267] In the above general formula (6), it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0268] In the above general formula (6), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not include a structure in which an oxygen atom is at the terminal, and contains an ether bond between carbon atoms. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. Also, the number is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0269] The monomer represented by the above general formula (6) is preferably at least one selected from the group consisting of monomers represented by the following general formulae (6a), (6b), (6c) and (6d). CF2=CF-O-(CF2) n1 -Y 3 (6a) (In the formula, n1 represents an integer of 1 to 10, and Y 3 -SO3M 1 Or -COOM 1 represents M 1 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, R 7 represents H or an organic group. CF2=CF-O-(CF2C(CF3)F) n2 -Y 3 (6b) (In the formula, n2 represents an integer of 1 to 5; Y 3 is the same as the above definition.) CF2=CF-O-(CFX 1 ) n3 -Y 3 (6c) (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, Y 3 is the same as the above definition.) CF2=CF-O-(CF2CFX 1 O) n4 -CF2CF2-Y 3 (6d) (In the formula, n4 represents an integer of 1 to 10; Y 3 and X 1 is the same as the above definition.)

[0270] In the formula (6a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. 3 -COOM is advantageous in that it provides adequate water solubility and stability of the aqueous dispersion. 1 It is preferable that M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0271] The perfluorovinyl alkyl compound represented by the above formula (6a) is, for example, CF2=CF-O-CF2COOM 1 (In the formula, M 1 is the same as above.)

[0272] In the above formula (6b), n2 is preferably an integer of 3 or less from the viewpoint of the stability of the resulting aqueous dispersion, and Y 3 -COOM has an advantage in that it provides adequate water solubility and stability of the aqueous dispersion. 1 It is preferable that M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0273] In the above formula (6c), n3 is preferably an integer of 5 or less in terms of water solubility, and Y 3-COOM has an advantage in that it provides adequate water solubility and stability of the aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4 in terms of improving dispersion stability.

[0274] In the above formula (6d), 1 is preferably -CF3 from the viewpoint of stability of the aqueous dispersion, n4 is preferably an integer of 5 or less from the viewpoint of water solubility, and Y 3 -COOM is advantageous in that it provides moderate water solubility and stability of aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4.

[0275] The perfluorovinyl ether compound represented by the above formula (6d) is, for example, CF2=CFOCF2CF(CF3)OCF2CF2COOM 1 (In the formula, M 1 represents H, NH4 or an alkali metal.

[0276] In the above general formula (7), Rf is preferably a fluorine-containing alkylene group having a carbon number of 1 to 40. In general formula (7), at least one of X and Y preferably contains a fluorine atom.

[0277] The monomer represented by the above general formula (7) is represented by the following general formula (7a): CF2=CF-(CF2) n1 -Y 3 (7a) (In the formula, n1 represents an integer of 1 to 10, and Y 3 is the same as defined above.) and a monomer represented by the following general formula (7b): CF2=CF-(CF2C(CF3)F) n2 -Y 3 (7b) (In the formula, n2 represents an integer of 1 to 5; Y 3 is as defined above. Preferably, at least one selected from the group consisting of monomers represented by Above Y3 -SO3M 1 Or -COOM 1 is preferred, M 1 is H, metal atom, NR 7 4. It is preferable that the R is 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.

[0278] In the formula (7a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. 3 -COOM is advantageous in that it provides adequate water solubility and stability of the aqueous dispersion. 1 It is preferable that M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved. The perfluorovinyl alkyl compound represented by the above formula (7a) is, for example, CF2=CFCF2COOM 1 (In the formula, M 1 is the same as above.)

[0279] In the above formula (7b), n2 is preferably an integer of 3 or less from the viewpoint of the stability of the resulting aqueous dispersion, and Y 3 -COOM has an advantage in that it provides adequate water solubility and stability of the aqueous dispersion. 1 It is preferable that M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0280] The content of the modified monomer (A) is preferably in the range of 0.00001 to 1.0% by mass. The lower limit is more preferably 0.0001% by mass, more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, even more preferably 0.10% by mass, and particularly preferably 0.05% by mass.

[0281] In the production of the TFE polymer, the polymer (1) can be used within the range of use in the production method of the present disclosure described above. The concentration of the polymer (1) is not particularly limited as long as it is within the above range, but is usually added at the start of polymerization at a critical micelle concentration (CMC) or less. If the amount added is large, needle-shaped particles with a large aspect ratio are generated, and the aqueous dispersion becomes gel-like, resulting in a loss of stability. The lower limit of the amount of the polymer (1) used is preferably 0.0001% by mass, more preferably 0.001% by mass, even more preferably 0.01% by mass, and particularly preferably 0.1% by mass, based on the aqueous medium. The upper limit of the amount of the polymer (1) used is preferably 10% by mass, more preferably 5% by mass, even more preferably 3% by mass, and particularly preferably 2% by mass, based on the aqueous medium.

[0282] The polymer (1) may be added to a reaction vessel all at once before the start of polymerization, or all at once after the start of polymerization, or may be added in several divided portions during polymerization, or may be added continuously during polymerization.

[0283] In the production of the TFE polymer, as the polymerization initiator, persulfates (e.g., ammonium persulfate), disuccinic acid peroxide, diglutaric acid peroxide, and other organic peroxides can be used alone or in the form of a mixture thereof. They may also be used in combination with a reducing agent such as sodium sulfite to form a redox system. Furthermore, during the polymerization, a radical scavenger such as hydroquinone or catechol, or a peroxide decomposer such as ammonium sulfite, can be added to adjust the radical concentration in the system.

[0284] As the redox polymerization initiator, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, and cerium ammonium nitrate. Examples of the reducing agent include sulfites, bisulfites, bromates, diimines, and oxalic acid. Examples of the persulfates include ammonium persulfate and potassium persulfate. Examples of the sulfites include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the combination of the redox initiator. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate.

[0285] Examples of the redox initiator include potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / iron sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / bisulfite, and the like, with potassium permanganate / oxalic acid being preferred. When using a redox initiator, either an oxidizing agent or a reducing agent may be charged in advance into a polymerization tank, and then the other may be added continuously or intermittently to initiate polymerization. For example, when potassium permanganate / oxalic acid is used, it is preferred to charge oxalic acid into a polymerization tank and continuously add potassium permanganate thereto.

[0286] In the production of the TFE polymer, known chain transfer agents can be used, for example, saturated hydrocarbons such as methane, ethane, propane, and butane; halogenated hydrocarbons such as chloromethane, dichloromethane, and difluoroethane; alcohols such as methanol and ethanol; and hydrogen. Among these, those that are in a gaseous state at normal temperature and pressure are preferred.

[0287] The amount of the chain transfer agent used is usually 1 to 10,000 ppm, and preferably 1 to 5,000 ppm, based on the total amount of TFE supplied. The amount may be 1 to 1,000 ppm, or 1 to 500 ppm.

[0288] In the production of the TFE polymer, a saturated hydrocarbon having 12 or more carbon atoms, which is substantially inert to the reaction and becomes liquid under the above reaction conditions, may be used as a dispersion stabilizer for the reaction system in an amount of 2 to 10 parts by mass per 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.

[0289] When the polymerization of the TFE polymer is completed, an aqueous dispersion having a solid content of 1.0 to 70% by mass and an average primary particle size of 50 to 500 nm can be obtained. The aqueous dispersion contains the polymer (1) and a fluoropolymer. By using the polymer (1), an aqueous dispersion having particles made of a TFE polymer with a fine particle size of 0.5 μm or less can be obtained. The lower limit of the solid content concentration is preferably 5% by mass, more preferably 8% by mass, and the upper limit is not particularly limited, but may be 40% by mass or 35% by mass. 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.

[0290] A fine powder can be produced by coagulating the aqueous dispersion. The aqueous dispersion of the TFE polymer can be used as a fine powder for various applications after coagulation, washing, and drying. When coagulating the aqueous dispersion of the TFE polymer, the aqueous dispersion obtained by polymerization of a polymer latex or the like is usually diluted with water to a polymer concentration of 10 to 20% by mass, and in some cases, the pH is adjusted to neutral or alkaline, and then the mixture is stirred more vigorously than during the reaction in a vessel equipped with a stirrer. The coagulation may be performed while stirring the mixture, while adding water-soluble organic compounds such as methanol and acetone, inorganic salts such as potassium nitrate and ammonium carbonate, and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid as a coagulant. The coagulation may also be performed continuously using an in-line mixer or the like.

[0291] The concentration of the unaggregated TFE polymer in the wastewater resulting from the aggregation is preferably low from the viewpoint of productivity, more preferably less than 0.4 mass %, particularly preferably less than 0.3 mass %.

[0292] By adding a pigment for coloring or various fillers for improving mechanical properties before or during the coagulation, a pigmented or filled TFE polymer fine powder in which the pigment and filler are uniformly mixed can be obtained.

[0293] The wet powder obtained by coagulating the aqueous dispersion of the TFE polymer is usually dried by using means such as vacuum, high frequency, hot air, etc., while keeping the wet powder in a state where it is not very fluid, preferably in a state where it is left still. Friction between powders, especially at high temperatures, generally has an undesirable effect on fine powder-type TFE polymers. This is because the particles made of this type of TFE polymer have the property of easily fibrillating even with a small shear force, and losing the original stable particle structure state.

[0294] The drying is carried out at a drying temperature of 10 to 250° C., preferably 100 to 250° C. The drying temperature may be 200° C. or lower.

[0295] The obtained TFE polymer fine powder is preferable for molding, and suitable applications include hydraulic and fuel system tubes for aircraft and automobiles, flexible hoses for chemical solutions, steam, etc., and wire coating applications.

[0296] The aqueous dispersion of the TFE polymer obtained by the above polymerization is preferably stabilized and further concentrated by adding a nonionic surfactant, and used in various applications as a composition to which an organic or inorganic filler is added depending on the purpose. The above composition, when applied to a substrate made of metal or ceramic, can provide a coating surface having non-adhesiveness and a low coefficient of friction, and excellent gloss, smoothness, abrasion resistance, weather resistance, and heat resistance, and is suitable for painting rolls, cooking utensils, etc., impregnation processing of glass cloth, etc.

[0297] The organosol of the TFE polymer can also be prepared from the aqueous dispersion. The organosol can contain the TFE polymer and an organic solvent, and the organic solvent can be an ether solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ester solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, or a halogenated hydrocarbon solvent, and N-methyl-2-pyrrolidone, dimethylacetamide, or the like can be suitably used. The organosol can be prepared, for example, by the method described in International Publication No. 2012 / 002038.

[0298] 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 aqueous dispersion or the fine powder is mixed with a host polymer or the like, thereby improving the melt strength during melt processing of the host polymer, and improving the mechanical strength, electrical properties, flame retardancy, anti-dripping property during burning, and sliding property of the obtained polymer.

[0299] The above-mentioned aqueous dispersion of the TFE polymer or the above-mentioned TFE polymer fine powder is also preferably used as a binder for batteries and for dust prevention purposes.

[0300] 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, for example, as described in JP-A-11-49912, U.S. Pat. No. 5,804,654, JP-A-11-29679, and JP-A-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.

[0301] The aqueous dispersion of the above-mentioned TFE polymer is also preferably mixed with the aqueous dispersion of melt-processable fluororesin to be coagulated to form coprecipitated powder.The above-mentioned coprecipitated powder is suitable as processing aid.

[0302] Examples of the melt-processable fluororesin include FEP, PFA, ETFE, and ethylene / TFE / HFP copolymer [EFEP], with FEP being preferred.

[0303] The aqueous dispersion preferably contains the melt-processable fluororesin. Examples of the melt-processable fluororesin include FEP, PFA, ETFE, and EFEP. The aqueous dispersion containing the melt-processable fluororesin can be used as a coating material. The melt-processable fluororesin can sufficiently fuse the particles of the TFE polymer together, improving film-forming properties and making the resulting coating glossy.

[0304] The fluorine-free resin that the above-mentioned co-coagulation powder is added to can be in powder form, pellet form, or emulsion form.The above-mentioned addition is preferably carried out while applying shear force by known methods such as extrusion kneading, roll kneading, etc., in order to thoroughly mix each resin.

[0305] The aqueous dispersion of the TFE polymer is also preferably used as a dust-suppressing treatment agent. The dust-suppressing treatment agent can be used in a method of mixing with a dust-generating substance and subjecting the mixture to a compression-shear action at a temperature of 20 to 200°C to fibrillate the TFE polymer and suppress the dust of the dust-generating substance, for example, in the methods described in Japanese Patent No. 2827152 and Japanese Patent No. 2538783. The above-mentioned aqueous dispersion of the TFE polymer can be suitably used in the dust suppression treatment composition described in, for example, WO 2007 / 004250, and can also be suitably used in the dust suppression treatment method described in WO 2007 / 000812.

[0306] The above-mentioned dust suppression treatment agent is suitably used for dust suppression treatment in the fields of building materials, soil stabilization materials, solidification materials, fertilizers, landfill disposal of incineration ash and harmful substances, explosion prevention, cosmetics, and sand for pet excretion, such as cat litter.

[0307] 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, which is a method in which the aqueous dispersion of the TFE polymer and the aqueous dispersion of a matrix polymer are mixed, the mixture is extruded to form an intermediate fiber structure, and the intermediate fiber structure is fired to decompose the matrix polymer and sinter the TFE polymer particles, thereby obtaining TFE polymer fibers.

[0308] The polymer (1) can also be used to produce high molecular weight PTFE. That is, the production method of the present disclosure using the polymer (1) can surprisingly produce PTFE without using a conventional fluorinated surfactant, and has a molecular weight equivalent to that of a production method using a conventional fluorinated surfactant.

[0309] The high molecular weight PTFE powder obtained by polymerization has extensibility and non-melt processability, and is also useful as a raw material for an extensible body (porous body). When this extensible body is a membrane (PTFE extensible membrane or PTFE porous membrane), it can be extensible by a known PTFE extensible method. By extensibility, the high molecular weight PTFE is easily fibrillated, and becomes a PTFE porous body (membrane) consisting of nodes and fibers. Preferably, a sheet-like or rod-like paste extrudate is roll-stretched in the extrusion direction to obtain a uniaxially stretched membrane. Furthermore, a biaxially stretched film can also be obtained by stretching the film in the width direction using a tenter or the like. It is also preferable to carry out a semi-baking treatment before stretching. The present disclosure also provides a method for producing an expanded body, comprising the step of expanding the polytetrafluoroethylene obtained by the above-mentioned production method. The expanding can be performed by any conventionally known PTFE expanding method and under any conditions, and is not limited thereto. The present disclosure also provides a method for producing a stretched body, comprising the steps of: obtaining polytetrafluoroethylene by polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (1) containing polymerization units (1) based on a monomer represented by the following general formula (1); and stretching the obtained polytetrafluoroethylene. CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom.

[0310] This expanded PTFE body is a porous body with a high porosity. The membrane can be suitably used as a filter medium for various precision filters such as air filters and chemical filters, and as a support material for polymer electrolyte membranes. They are also useful as materials for products used in the fields of textiles, medicine, electrochemicals, sealing materials, air filtration, ventilation / internal pressure regulation, liquid filtration, and general consumer goods. Specific applications are given below as examples.

[0311] Electrochemical Field Dielectric material prepreg, EMI shielding material, heat transfer material, etc. More specifically, printed wiring board, electromagnetic shielding material, insulating heat transfer material, insulating material, etc. Sealing materials field Gaskets, packing, pump diaphragms, pump tubes, aircraft sealing materials, etc.

[0312] Air Filtration Field ULPA filters (for semiconductor manufacturing), HEPA filters (for hospitals and semiconductor manufacturing), cylindrical cartridge filters (for industrial use), bag filters (for industrial use), heat-resistant bag filters (for exhaust gas treatment), heat-resistant pleated filters (for exhaust gas treatment), SINBRAN filters (for industrial use), catalyst filters (for exhaust gas treatment), adsorbent filters (for HDD installation), adsorbent vent filters (for HDD installation), vent filters (for HDD installation and others), vacuum cleaner filters (for vacuum cleaners), general-purpose multi-layer felt material, GT cartridge filters (for GT compatible products), cooling filters (for electronic equipment housings), etc.

[0313] Ventilation / internal pressure regulation field Freeze-drying materials such as freeze-drying containers, automotive ventilation materials for electronic circuits and lamps, container applications such as container caps, protective ventilation applications for electronic devices including small terminals such as tablet terminals and mobile phones, medical ventilation applications, etc.

[0314] Liquid Filtration Semiconductor liquid filtration filters (for semiconductor manufacturing), hydrophilic PTFE filters (for semiconductor manufacturing), chemical filters (for chemical liquid treatment), pure water production line filters (for pure water production), backwash type liquid filtration filters (for industrial wastewater treatment), etc.

[0315] General consumer goods field Clothing, cable guides (movable wires for motorcycles), motorcycle clothing, cast liners (medical supporters), vacuum cleaner filters, bagpipes (musical instruments), cables (signal cables for guitars, etc.), strings (for stringed instruments), etc.

[0316] Textiles PTFE fiber (textile material), sewing thread (textile), weaving thread (textile), rope, etc.

[0317] Medical field Internal implants (extended products), artificial blood vessels, catheters, general surgery (tissue reinforcement materials), head and neck products (dura substitutes), oral health (tissue regenerative medicine), orthopedics (bandages), etc.

[0318] The above polymer (1) can also be used to produce low molecular weight PTFE. The low molecular weight PTFE may be produced by polymerization, or it may be produced by lowering the molecular weight of the high molecular weight PTFE obtained by polymerization by a known method (thermal decomposition, decomposition by irradiation, etc.).

[0319] Low-molecular-weight PTFE (also called PTFE micropowder) having a molecular weight of 600,000 or less has excellent chemical stability, extremely low surface energy, and is not prone to fibrillation. Therefore, it is suitable as an additive for improving the slipperiness and texture of coating surfaces in the production of plastics, inks, cosmetics, paints, greases, office automation equipment components, toners, and the like (see, for example, JP-A-10-147617).

[0320] Furthermore, a polymerization initiator and the above polymer (1) may be dispersed in an aqueous medium in the presence of a chain transfer agent, and TFE or a monomer copolymerizable with TFE may be polymerized with TFE to obtain a low molecular weight PTFE.

[0321] When the low-molecular-weight PTFE obtained by the above polymerization is used as a powder, the above aqueous dispersion can be coagulated to form powder particles.

[0322] In the present disclosure, high molecular weight PTFE refers to non-melt processable and fibrillating PTFE, whereas low molecular weight PTFE refers to melt processable and non-fibrillating PTFE.

[0323] The above-mentioned non-melt processability means that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point according to ASTM D-1238 and D-2116.

[0324] The presence or absence of fibrillation properties can be judged by "paste extrusion," a typical method for molding "high molecular weight PTFE powder," a powder made from a TFE polymer. Paste extrusion is usually possible because high molecular weight PTFE has fibrillation properties. If the unsintered molded product obtained by paste extrusion has no substantial strength or elongation, for example, if it breaks when pulled with an elongation of 0%, it can be considered to have no fibrillation properties.

[0325] The high molecular weight PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.280. The standard specific gravity is measured by a water displacement method in accordance with ASTM D-792 using a sample molded in accordance with ASTM D4895-89. In the present disclosure, "high molecular weight" means that the standard specific gravity is within the above range.

[0326] The above low molecular weight PTFE has a complex viscosity of 1×10 at 380°C. 2 ~7×10 5 In this disclosure, "low molecular weight" means that the complex viscosity is within the above range.

[0327] The complex viscosity of the high molecular weight PTFE is much higher than that of the low molecular weight PTFE, and it is difficult to measure the complex viscosity accurately. On the other hand, although the complex viscosity of the low molecular weight PTFE can be measured, it is difficult to obtain a molded product that can be used to measure the standard specific gravity from the low molecular weight PTFE, and it is difficult to measure the standard specific gravity accurately. Therefore, in this disclosure, the standard specific gravity is adopted as an index of the molecular weight of the high molecular weight PTFE, and the complex viscosity is adopted as an index of the molecular weight of the low molecular weight PTFE. Note that there is no known measurement method that can directly specify the molecular weight of either the high molecular weight PTFE or the low molecular weight PTFE.

[0328] The high molecular weight PTFE preferably has a peak temperature of 333 to 347° C., more preferably 335 to 345° C. The low molecular weight PTFE preferably has a peak temperature of 322 to 333° C., more preferably 324 to 332° C. The peak temperature is the temperature corresponding to the maximum value in the heat of fusion curve when PTFE that has no history of being heated to a temperature of 300° C. or higher is heated at a rate of 10° C. / min using a differential scanning calorimeter [DSC].

[0329] The high molecular weight PTFE preferably has at least one endothermic peak in the range of 333 to 347°C in a heat of fusion curve obtained by heating PTFE that has not been heated to a temperature of 300°C or higher at a rate of 10°C / min using a differential scanning calorimeter [DSC], and has a heat of fusion of 62 mJ / mg or more at 290 to 350°C calculated from the heat of fusion curve.

[0330] An unsintered tape (green tape) can also be obtained from the PTFE fine powder obtained by using the above polymer (1).

[0331] The polymer (1), by-products produced from the polymer (1), residual monomers, etc. may be recovered and purified from the wastewater generated by the coagulation or washing and / or the off-gas generated in the drying step, so that the polymer (1), by-products produced from the polymer (1), residual monomers, etc. can be reused. The method for the recovery and purification is not particularly limited, and can be carried out by a known method. For example, it can be carried out by the method described in JP-A-2011-520020.

[0332] (II) Melt-processable fluororesin (1) In the production method of the present disclosure, the polymerization of FEP is preferably carried out at a polymerization temperature of 10 to 150° C. and a polymerization pressure of 0.3 to 6.0 MPaG.

[0333] The preferred monomer composition (mass%) of FEP is TFE:HFP=(60-98):(2-40), more preferably (60-95):(5-40), and even more preferably (85-92):(8-15). The FEP may be modified with a perfluoro(alkyl vinyl ether) as a third component within the range of 0.1-2 mass% of the total monomers.

[0334] In the polymerization of the FEP, the polymer (1) can be used within the range of use in the production method of the present disclosure, but is usually added in an amount of 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium.

[0335] In the above-mentioned polymerization of FEP, it is preferable to use, as the chain transfer agent, cyclohexane, methanol, ethanol, propanol, ethane, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, or the like, and it is preferable to use, as the pH buffer agent, ammonium carbonate, disodium hydrogen phosphate, or the like.

[0336] The aqueous dispersion of FEP obtained by the manufacturing method of the present disclosure may be subjected to post-treatment such as concentration as necessary, dried, powdered, and then melt-extruded to form pellets. The aqueous medium in the aqueous dispersion of FEP may contain additives such as a nonionic surfactant as necessary, but may also contain a water-soluble organic solvent such as a water-soluble alcohol, or may not contain a water-soluble organic solvent.

[0337] Furthermore, the melt extrusion can be carried out by appropriately setting the extrusion conditions so long as the extrusion conditions generally enable pelletization.

[0338] In the manufacturing method of the present disclosure, the obtained FEP may have terminal groups such as -CF3, -CF2H at at least one site of the polymer main chain and / or the polymer side chain, but it is preferable that the content of thermally unstable groups such as -COOH, -CH2OH, -COF, -CF=CF-, -CONH2, -COOCH3 (hereinafter referred to as "unstable terminal groups") is low or absent.

[0339] The unstable terminal groups are chemically unstable and therefore not only reduce the heat resistance of the resin but also cause an increase in the attenuation of the resulting electric wire.

[0340] In the production method of the present disclosure, the polymer at the end of polymerization is prepared by subjecting the polymer to a polymerization reaction in which the total number of unstable terminal groups and -CF2H terminal groups is 1×10 6 It is preferable to produce the cyclopentasiloxane so that the number of carbon atoms per unit is 50 or less. More preferably, the number of carbon atoms per unit is 1×10 6 The number per unit is preferably less than 20, and more preferably not more than 5. The unstable terminal group and the -CF2H terminal group may be absent, and all the terminal groups may be -CF3 terminal groups.

[0341] The unstable terminal group and -CF2H terminal group can be stabilized by converting them to -CF3 terminal groups by fluorination treatment. The fluorination treatment method is not particularly limited, but may be a method of exposing the polymer to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions. Examples of the fluorine radical source include fluorine gas, CoF3, AgF2, UF6, OF2, N2F2, CF3OF, and halogen fluorides such as IF5 and ClF3. Among them, a method of directly contacting the fluorination gas with the FEP obtained by the present disclosure is preferred, and the contact is preferably performed using a diluted fluorine gas having a fluorine gas concentration of 10 to 50 mass% in terms of reaction control. The diluted fluorine gas can be obtained by diluting fluorine gas with an inert gas such as nitrogen gas or argon gas. The fluorine gas treatment can be performed at a temperature of, for example, 100 to 250°C. The treatment temperature is not limited to the above range and can be appropriately set depending on the situation. The fluorine gas treatment is preferably performed by continuously or intermittently supplying diluted fluorine gas into a reactor. The fluorination treatment may be performed on a dry powder after polymerization or on melt-extruded pellets.

[0342] The FEP obtained by the manufacturing method of the present disclosure has good moldability and is less prone to molding defects, as well as good heat resistance, chemical resistance, solvent resistance, insulating properties, electrical properties, and the like.

[0343] The method for producing the above-mentioned FEP powder is a method for obtaining a powder by drying and pulverizing the FEP obtained by the production method of the present disclosure described above.

[0344] The powder may be fluorinated. The method for producing the fluorinated powder is a method for obtaining the fluorinated powder by supplying fluorine gas to the powder obtained by the method for producing the powder described above to fluorinate the powder.

[0345] The method for producing FEP pellets is a method for obtaining pellets by pelletizing the FEP obtained by the production method of the present disclosure described above.

[0346] The pellets may be fluorinated. The method for producing fluorinated pellets is a method for obtaining fluorinated pellets by supplying fluorine gas to the pellets obtained by the above-mentioned method for producing pellets, thereby fluorinating the pellets.

[0347] Therefore, this FEP can be used to produce various molded products, such as covering materials for electric wires, foamed electric wires, cables, wires, etc., as well as tubes, films, sheets, filaments, etc.

[0348] (2) In the production method of the present disclosure, the polymerization of a TFE / perfluoro(alkyl vinyl ether) copolymer such as PFA or MFA is usually preferably carried out at a polymerization temperature of 10 to 100° C. and a polymerization pressure of 0.3 to 6.0 MPaG.

[0349] 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). The perfluoro(alkyl vinyl ether) is represented by the formula: CF2=CFORf 4 (In the formula, Rf 4 It is preferable to use one represented by a perfluoroalkyl group having 1 to 6 carbon atoms.

[0350] In the polymerization of the TFE / perfluoro(alkyl vinyl ether) copolymer, the polymer (1) can be used within the range of use in the production method of the present disclosure, but it is usually preferable to add it in an amount of 0.0001 to 10 mass % relative to 100 mass % of the aqueous medium.

[0351] In the polymerization of the above TFE / perfluoro(alkyl vinyl ether) copolymer, it is preferable to use cyclohexane, methanol, ethanol, propanol, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, methane, ethane, or the like as a chain transfer agent, and it is preferable to use ammonium carbonate, disodium hydrogen phosphate, or the like as a pH buffer.

[0352] The aqueous dispersion of TFE / perfluoro(alkyl vinyl ether) copolymer such as PFA or MFA obtained by the manufacturing method of the present disclosure may be subjected to post-treatment such as concentration as necessary, dried, powdered, and then melt-extruded to form pellets. The aqueous medium in the aqueous dispersion may contain additives such as nonionic surfactants as necessary, but may also contain a water-soluble organic solvent such as a water-soluble alcohol, or may not contain a water-soluble organic solvent.

[0353] Furthermore, the melt extrusion can be carried out by appropriately setting the extrusion conditions so long as the extrusion conditions generally enable pelletization.

[0354] The above copolymer is preferably subjected to a fluorine gas treatment in order to improve its heat resistance and further strengthen the effect of suppressing the permeation of chemical solutions into the molded article.

[0355] The fluorine gas treatment is carried out by contacting the fluorine gas with the chemical liquid permeation inhibitor. However, since the reaction with fluorine is very exothermic, it is preferable to dilute the fluorine with an inert gas such as nitrogen. The amount of fluorine in the fluorine gas / inert gas mixture is 1 to 100% by weight, preferably 10 to 25% by weight. The treatment temperature is 150 to 250°C, preferably 200 to 250°C, and the fluorine gas treatment time is 3 to 16 hours, preferably 4 to 12 hours. The gas pressure for the fluorine gas treatment is in the range of 1 to 10 atm, but atmospheric pressure is preferably used. When the reactor is used at atmospheric pressure, the fluorine gas / inert gas mixture may be continuously passed through the reactor. As a result, the unstable terminals of the copolymer are converted to -CF3 terminals, which become thermally stable.

[0356] As for the molding method of the above copolymer and its composition, similar to that of conventional PFA, molding methods such as compression molding, transfer molding, extrusion molding, injection molding, blow molding, etc. can be applied.

[0357] By such molding methods, desired molded products can be obtained, and examples of the molded products include sheets, films, packings, round bars, square bars, pipes, tubes, round tanks, square tanks, tanks, wafer carriers, wafer boxes, beakers, filter housings, flow meters, pumps, valves, cocks, connectors, nuts, electric wires, heat-resistant electric wires, etc.

[0358] Among these, the material can be suitably used for tubes, pipes, tanks, connectors, etc. used in various chemical reaction equipment, semiconductor manufacturing equipment, and acid or alkaline chemical supply equipment, which require impermeability to chemicals.

[0359] Furthermore, a primer composition can be obtained by adding a nonionic surfactant to an aqueous dispersion of a TFE / perfluoro(alkyl vinyl ether) copolymer such as PFA or MFA, and dissolving or dispersing polyethersulfone, polyamideimide and / or polyimide, and metal powder in an organic solvent as necessary. This primer composition can also be used in a method for coating a metal surface with a fluororesin, which comprises applying the primer composition to a metal surface, applying a melt-processable fluororesin composition onto the thus-formed primer layer, and baking the melt-processable fluororesin composition layer together with the primer layer.

[0360] (3) In the production method of the present disclosure, the polymerization of ETFE is preferably carried out at a polymerization temperature of 10 to 100° C. and a polymerization pressure of 0.3 to 2.0 MPaG.

[0361] The preferred monomer composition (mol%) of ETFE is TFE:ethylene=(50-99):(50-1). The ETFE may be modified by further using a third monomer within the range of 0-20 mass% of the total monomers. The preferred ratio is TFE:ethylene:third monomer=(63-94):(27-2):(1-10). The preferred third monomer is perfluorobutylethylene, perfluorobutylethylene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene, 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH2=CFCF2CF2CF2H), or 2-trifluoromethyl-3,3,3-trifluoropropene ((CF3)2C=CH2).

[0362] In the polymerization of ETFE, the polymer (1) can be used within the range of use in the production method of the present disclosure, but is usually added in an amount of 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium.

[0363] In the above polymerization of ETFE, it is preferable to use, as a chain transfer agent, cyclohexane, methanol, ethanol, propanol, ethane, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, or the like.

[0364] The aqueous dispersion of ETFE obtained by the manufacturing method of the present disclosure may be subjected to post-treatment such as concentration as necessary, dried, powdered, and then melt-extruded to form pellets. The aqueous medium in the aqueous dispersion may contain additives such as a nonionic surfactant as necessary, but may also contain a water-soluble organic solvent such as a water-soluble alcohol, or may not contain a water-soluble organic solvent.

[0365] Furthermore, the melt extrusion can be carried out by appropriately setting the extrusion conditions so long as the extrusion conditions generally enable pelletization.

[0366] The ETFE sheet can be extruded into a sheet. That is, ETFE powder or pellets can be melted, extruded continuously through a die, and cooled to obtain a sheet-like molded product. Additives may be added to the ETFE.

[0367] As the additive, known additives can be appropriately used. Specific examples include ultraviolet absorbers, light stabilizers, antioxidants, infrared absorbers, flame retardants, flame-retardant fillers, organic pigments, inorganic pigments, dyes, etc. Inorganic additives are preferred from the viewpoint of excellent weather resistance. 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.

[0368] The above-mentioned ETFE sheet has excellent mechanical strength and appearance, and is therefore suitable as a membrane material (roofing material, ceiling material, exterior wall material, interior wall material, covering material, etc.) for membrane structure buildings (sports facilities, horticultural facilities, atriums, etc.). In addition to being useful as a membrane material for membrane-structured buildings, it is also useful for, for example, outdoor-use board materials (soundproof walls, windbreak fences, wave-overtopping fences, garage canopies, shopping malls, walkway walls, roofing materials), glass shatterproof films, heat-resistant and water-resistant sheets, building materials (tent materials for tent warehouses, sunshade membrane materials, partial roof materials for lighting, window materials to replace glass, fireproof partition membrane materials, curtains, exterior wall reinforcement, waterproof membranes, smoke-proof membranes, non-flammable transparent partitions, road reinforcement, interiors (lighting, walls, brands, etc.), exteriors (tents, signs, etc.), etc.), daily leisure goods (fishing rods, rackets, golf clubs, projection screens, etc.), automobile materials (tops, vibration-damping materials, bodies, etc.), aircraft materials, ship materials, home appliance exteriors, tanks, container inner walls, filters, construction membrane materials, electronic materials (printed circuit boards, wiring boards, insulating films, release films, etc.), surface materials for solar cell modules, mirror protective materials for solar thermal power generation, surface materials for solar water heaters, etc.

[0369] (4) The manufacturing method of the present disclosure can also be used to manufacture an electrolyte polymer precursor. In the manufacturing method of the present disclosure, the polymerization of the electrolyte polymer precursor is preferably carried out at a polymerization temperature of 10 to 100°C and a polymerization pressure of 0.1 to 2.0 MPaG. The electrolyte polymer precursor is made of a vinyl ether monomer as shown below, and can be converted into an ion-exchange polymer through a hydrolysis treatment.

[0370] Examples of vinyl ether monomers used in the electrolyte polymer precursor include: General formula (150): CF2=CF-O-(CF2CFY 151 -O) n -(CFY 152 ) m -A 151 (In the formula, Y 151 represents a fluorine atom, a chlorine atom, a -SO2F group, or a perfluoroalkyl group. The perfluoroalkyl group may contain an etheric oxygen and a -SO2F group. n represents an integer of 0 to 3. n Y 151 may be the same or different. Y 152 represents a fluorine atom, a chlorine atom, or a -SO2F group. m represents an integer of 1 to 5. m Y 152may be the same or different. A 151 -SO2X 151 , -COZ 151 or -POZ 152 Z 153 Represents X. 151 is F, Cl, Br, I, -OR 151 or -NR 152 R 153 Represents Z. 151 , Z 152 and Z 153 are the same or different, -NR 154 R 155 -OR 156 Represents R 151 , R 152 , R 153 , R 154 , R 155 and R 156 are the same or different and represent H, ammonium, an alkali metal, an alkyl group which may contain a fluorine atom, an aryl group, or a sulfonyl-containing group.) A 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).

[0371] The electrolyte polymer precursor may be modified with a third monomer within a range of 0 to 20% by mass of the total monomers. Examples of the third monomer include polyfunctional monomers such as CTFE, vinylidene fluoride, perfluoroalkyl vinyl ether, and divinylbenzene.

[0372] The electrolyte polymer precursor thus obtained can be formed into a membrane, for example, and then subjected to hydrolysis with an alkaline solution and treatment with a mineral acid to form a polymer electrolyte membrane, which can be used in fuel cells, electrolysis devices, redox flow batteries, and the like. Moreover, by subjecting the electrolyte polymer precursor to hydrolysis with an alkaline solution while maintaining the dispersed state of the electrolyte polymer precursor, an electrolyte polymer dispersion can be obtained. Subsequently, by heating to 120° C. or higher in a pressurized vessel, the compound can be dissolved in, for example, a water / alcohol mixed solvent to form a solution. The solution thus obtained can be used, for example, as a binder for electrodes, or can be combined with various additives to form a cast film, which can be used, for example, for an antifouling coating film or an organic actuator.

[0373] (5)TFE / VDF copolymer In the production method of the present disclosure, the polymerization temperature for 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, but may usually be 0 to 9.8 MPaG.

[0374] The preferred monomer composition (mol%) of the TFE / VDF copolymer is TFE:VDF=(5-90):(95-10). The TFE / VDF copolymer may also be modified with a third monomer within the range of 0-50 mol% of the total monomers. Preferably, the ratio is TFE:ethylene:third monomer=(30-85):(10-69.9):(0.1-10).

[0375] The third monomer is Formula: CX 11 X 12 =CX 13 (CX 14 X 15 ) n11 X 16 (In the formula, X 11 ~X 16 are the same or different and represent H, F or Cl, and n11 represents an integer of 0 to 8, except for TFE and VDF, or Formula: CX 21 X 22 =CX 23 -O(CX 24 X 25 ) n21 X 26 (In the formula, X 21 ~X 26are the same or different and represent H, F or Cl, and n21 represents an integer of 0 to 8.) is preferred.

[0376] The third monomer may be a fluorine-free ethylenic monomer. The fluorine-free ethylenic monomer is preferably selected from ethylenic monomers having 6 or less carbon atoms in terms of maintaining heat resistance and chemical resistance. Examples of the fluorine-free ethylenic monomer include ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, alkyl vinyl ether (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, and methacrylic acid.

[0377] In the polymerization of the TFE / VDF copolymer, the above polymer (1) can be used within the range of use in the production method of the present disclosure, but is usually added in an amount of 0.0001 to 5% by mass relative to 100% by mass of the aqueous medium.

[0378] The TFE / VDF copolymer obtained by polymerization may be subjected to an amidation treatment by contacting it with aqueous ammonia, ammonia gas, or a nitrogen compound capable of generating ammonia.

[0379] The TFE / VDF copolymer obtained by the above-mentioned method is also preferably used as a raw material for obtaining a TFE / VDF copolymer fiber by a spinning and drawing method, in which the TFE / VDF copolymer is melt-spun and then cooled and solidified to obtain an undrawn yarn, and the undrawn yarn is then run through a heating cylinder to draw the undrawn yarn, thereby obtaining a TFE / VDF copolymer fiber.

[0380] The TFE / VDF copolymer can 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 mixtures thereof. The solution can be used as a binder for batteries.

[0381] It is also preferable to coat the aqueous dispersion of the TFE / VDF copolymer on a porous substrate made of a polyolefin resin and use it as a composite porous membrane. It is also preferable to disperse inorganic particles and / or organic particles in the aqueous dispersion and coat it on a porous substrate and use it as a composite porous membrane. The composite porous membrane thus obtained can be used as a separator for a lithium secondary battery, etc.

[0382] The melt-processable fluororesin powder can be suitably used as a powder coating material. When a powder coating material made of the melt-processable fluororesin powder is applied to a substrate, a coating film with a smooth surface can be obtained. The melt-processable fluororesin powder having an average particle size of 1 μm or more and less than 100 μm is particularly suitable as a powder coating material used for electrostatic coating, and the melt-processable fluororesin powder having an average particle size of 100 μm or more and 1000 μm or less is particularly suitable as a powder coating material used for rotational coating or rotational molding.

[0383] The melt-processible fluororesin powder can be produced by drying and powdering the melt-processible fluororesin obtained by the production method of the present disclosure. The production method for producing the melt-processible fluororesin powder is also one aspect of the present disclosure.

[0384] (III) Fluorine rubber In the manufacturing method of the present disclosure, the polymerization of the fluororubber is carried out by charging pure water and the polymer (1) into a pressure-resistant reaction vessel equipped with a stirrer, deoxidizing, charging monomer, bringing the temperature to a predetermined level, and adding a polymerization initiator to start the reaction. As the pressure decreases as the reaction proceeds, additional monomer is continuously or intermittently supplied to maintain the initial pressure. When a predetermined amount of monomer has been supplied, the supply is stopped, the monomer in the reaction vessel is purged, and the temperature is returned to room temperature to terminate the reaction. In this case, the polymer latex can be continuously removed from the reaction vessel.

[0385] In particular, when producing a thermoplastic elastomer as the fluororubber, as disclosed in International Publication No. 00 / 01741, it is possible to use a method in which fluoropolymer fine particles are first synthesized at a high concentration as described above, then diluted and further polymerized, thereby making it possible to increase the final polymerization rate compared to normal polymerization.

[0386] The polymerization conditions for the fluororubber are appropriately selected from the viewpoints of the physical properties of the target polymer and control of the polymerization rate, and the polymerization temperature is usually -20 to 200°C, preferably 5 to 150°C, and the polymerization pressure is usually 0.5 to 10 MPaG, preferably 1 to 7 MPaG. The pH of the polymerization medium is preferably maintained at 2.5 to 13 by a known method or the like using a pH adjuster described below.

[0387] In addition to vinylidene fluoride, the monomers used in the polymerization of the fluororubber include fluorine-containing ethylenically unsaturated monomers that have at least the same number of fluorine atoms as carbon atoms and can be copolymerized with vinylidene fluoride. The fluorine-containing ethylenically unsaturated monomers include trifluoropropene, pentafluoropropene, hexafluorobutene, and octafluorobutene. Among them, hexafluoropropene is particularly suitable due to the properties of the elastomer obtained when it blocks the crystal growth of the polymer. The fluorine-containing ethylenically unsaturated monomers also include trifluoroethylene, TFE, and CTFE, and fluorine-containing monomers having one or more chlorine and / or bromine substituents can also be used. Perfluoro(alkyl vinyl ethers), such as perfluoro(methyl vinyl ether), can also be used. TFE and HFP are preferred for producing fluororubbers.

[0388] The preferred monomer composition (mass%) of the fluororubber is vinylidene fluoride:HFP:TFE=(20-70):(20-48):(0-32), more preferably (20-70):(30-48):(0-32), and even more preferably (32-64):(30-48):(0-27). The fluororubber of this composition exhibits good elastomer properties, chemical resistance, and thermal stability.

[0389] In the polymerization of the fluororubber, the polymer (1) can be used within the range of use in the production method of the present disclosure, but 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.

[0390] In the polymerization of the fluororubber, a known inorganic radical polymerization initiator can be used as the polymerization initiator. As the inorganic radical polymerization initiator, a conventionally known water-soluble inorganic peroxide, for example, sodium, potassium and ammonium persulfate, perphosphate, perborate, percarbonate or permanganate, is particularly useful. The radical polymerization initiator can be further activated by a reducing agent, for example, sodium, potassium or ammonium sulfite, bisulfite, metabisulfite, hyposulfite, thiosulfate, phosphite or hypophosphite, or by an easily oxidized metal compound, for example, ferrous salt, cuprous salt or silver salt. A suitable inorganic radical polymerization initiator is ammonium persulfate, and it is more preferable to use it in a redox system together with ammonium persulfate and sodium bisulfite.

[0391] The concentration of the polymerization initiator added is appropriately determined depending on the molecular weight of the desired fluoropolymer and the polymerization reaction rate, but is set to an amount of 0.0001 to 10 mass %, preferably 0.01 to 5 mass %, relative to 100 mass % of the total amount of monomers.

[0392] In the polymerization of the fluororubber, known chain transfer agents can be used, including hydrocarbons, esters, ethers, alcohols, ketones, chlorine compounds, carbonates, etc., and in the polymerization of the thermoplastic elastomer, hydrocarbons, esters, ethers, alcohols, chlorine compounds, iodine compounds, etc. Among these, acetone and isopropyl alcohol are preferred, and in the polymerization of the thermoplastic elastomer, isopentane, diethyl malonate, and ethyl acetate are preferred from the viewpoint of being less likely to cause a decrease in reaction rate, and diiodine compounds such as I(CF2)4I, I(CF2)6I, and ICH2I are preferred from the viewpoint of being capable of iodinating the polymer terminals and being usable as reactive polymers.

[0393] The amount of the chain transfer agent used is usually 0.5×10 -3 ~5×10 -3 mol%, preferably 1.0×10 -3~3.5×10 -3 It is preferably expressed as mol %.

[0394] In the polymerization of the fluororubber, paraffin wax or the like can be preferably used as a stabilizer, and in the polymerization of the thermoplastic elastomer, phosphates, sodium hydroxide, potassium hydroxide or the like can be preferably used as a pH adjuster.

[0395] The fluororubber obtained by the production method of the present disclosure has a solid content of 1.0 to 40 mass %, 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 at the time when polymerization is completed.

[0396] The fluororubber obtained by the manufacturing method of the present disclosure can be made into a dispersion suitable for rubber molding processing by adding a dispersion stabilizer such as a hydrocarbon surfactant, concentrating, etc., as necessary. The dispersion is treated by pH adjustment, coagulation, heating, etc. Each treatment is performed as follows.

[0397] The pH adjustment is performed by adding a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid, and / or a carboxylic acid having 5 or less carbon atoms and a pK of 4.2 or less to adjust the pH to 2 or less.

[0398] The coagulation is carried out by adding alkaline earth metal salts, such as nitrates, chlorates and acetates of calcium or magnesium.

[0399] Either the pH adjustment or the coagulation may be carried out first, but it is preferable to carry out the pH adjustment first.

[0400] After each operation, the fluororubber is washed with the same volume of water as the fluororubber to remove impurities such as small amounts of buffer solution and salts present in the fluororubber, and then dried. Drying is usually performed in a drying oven at high temperature, about 70 to 200°C, with air circulating.

[0401] The fluororubber may be a partially fluorinated rubber or a perfluororubber.

[0402] Examples of partially fluorinated rubber include 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 these, at least one selected from the group consisting of vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber is preferable.

[0403] The vinylidene fluoride-based fluororubber is preferably a copolymer consisting of 45 to 85 mol % of vinylidene fluoride and 55 to 15 mol % of at least one other monomer copolymerizable with vinylidene fluoride, more preferably a copolymer consisting of 50 to 80 mol % of vinylidene fluoride and 50 to 20 mol % of at least one other monomer copolymerizable with vinylidene fluoride.

[0404] Examples of at least one other monomer copolymerizable with the vinylidene fluoride include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, and the general formula (100): CH2=CFRf 101 (In the formula, Rf 101 is a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluoromonomer represented by the general formula (170): CH2=CH-(CF2) n -X 171 (In the formula, X171 is H or F, and n is an integer of 3 to 10.) and monomers such as monomers that provide crosslinking sites; and non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ethers. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether, and CTFE. As the fluoroalkyl vinyl ether, a fluoromonomer represented by the general formula (160) is preferable.

[0405] 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 / fluoromonomer-based rubbers represented by general formula (100), VDF / fluoromonomer / TFE-based rubbers represented by general formula (100), VDF / perfluoro(methyl vinyl ether) [PMVE]-based rubbers, VDF / PMVE / TFE-based rubbers, VDF / PMVE / TFE / HFP-based rubbers, etc. As the VDF / fluoromonomer-based rubbers represented by general formula (100), VDF / CH2=CFCF3-based rubbers are preferred, and as the VDF / fluoromonomer / TFE-based rubbers represented by general formula (100), VDF / TFE / CH2=CFCF3-based rubbers are preferred.

[0406] The VDF / CH2=CFCF3 rubber is preferably a copolymer consisting of 40 to 99.5 mol % of VDF and 0.5 to 60 mol % of CH2=CFCF3, and more preferably a copolymer consisting of 50 to 85 mol % of VDF and 20 to 50 mol % of CH2=CFCF3.

[0407] The above-mentioned tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer consisting of 45 to 70 mol % of tetrafluoroethylene, 55 to 30 mol % of propylene, and 0 to 5 mol % of a fluoromonomer that provides a crosslinking site.

[0408] The fluororubber may be a perfluororubber. The perfluororubber is preferably at least one selected from the group consisting of perfluororubbers containing TFE, such as TFE / fluoromonomer copolymers represented by general formula (160), (130) or (140) and TFE / fluoromonomer copolymers providing crosslinking sites represented by general formula (160), (130) or (140).

[0409] In the case of a TFE / PMVE copolymer, the composition is preferably 45-90 / 10-55 (mol %), more preferably 55-80 / 20-45, and further preferably 55-70 / 30-45.

[0410] In the case of a copolymer of TFE / PMVE / monomer that provides a crosslinking site, the ratio 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 even more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.

[0411] In the case of a fluoromonomer copolymer having 4 to 12 carbon atoms and represented by 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, and even more preferably 65 to 85 / 15 to 35.

[0412] In the case of TFE / fluoromonomer having 4 to 12 carbon atoms and represented by general formula (160), (130) or (140) / monomer copolymer 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 even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3.

[0413] Outside these composition ranges, the rubber elastic properties are lost and the properties tend to become more like those of a resin.

[0414] The perfluororubber is preferably at least one selected from the group consisting of TFE / fluoromonomer copolymer represented by general formula (140) / which provides a crosslinking moiety, TFE / perfluorovinyl ether copolymer represented by general formula (140), TFE / fluoromonomer copolymer represented by general formula (160), and TFE / fluoromonomer copolymer representing general formula (160) / which provides a crosslinking moiety.

[0415] Examples of the perfluororubber include those described in International Publication No. 97 / 24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, and Japanese Patent Publication No. 5-13961.

[0416] The fluororubber has a glass transition temperature of preferably −70° C. or higher, more preferably −60° C. or higher, and even more preferably −50° C. or higher, from the viewpoint of excellent compression set at high temperatures. Also, from the viewpoint of good cold resistance, the glass transition temperature is preferably 5° C. or lower, more preferably 0° C. or lower, and even more preferably −3° C. or lower.

[0417] The glass transition temperature can be determined by obtaining a DSC curve using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo) by heating 10 mg of a sample at a rate of 10°C / min, and by determining the temperature that indicates the midpoint between the two intersection points of an extension of the baseline before and after the second-order transition of the DSC curve and a tangent to the inflection point of the DSC curve.

[0418] In terms of good heat resistance, the fluororubber preferably has a Mooney viscosity ML(1+20) at 170°C of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In terms of good processability, the Mooney viscosity ML(1+20) is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

[0419] In terms of good heat resistance, the fluororubber preferably has a Mooney viscosity ML(1+20) at 140°C of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In terms of good processability, the Mooney viscosity ML(1+20) is preferably 180 or less, more preferably 150 or less, and even more preferably 110 or less.

[0420] In terms of good heat resistance, the fluororubber preferably has a Mooney viscosity ML(1+10) at 100°C of 10 or more, more preferably 20 or more, and even more preferably 30 or more. In terms of good processability, the Mooney viscosity ML(1+10) is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0421] The Mooney viscosity can be measured using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES at 170° C., 140° C. or 100° C. in accordance with JIS K6300.

[0422] The fluororubber obtained by the production method of the present disclosure may be in any form as long as it is obtained from the above polymerization, and may be an aqueous dispersion after polymerization, or may be used as a gum or crumb obtained by coagulating, drying, etc., the aqueous dispersion after polymerization by a conventionally known method. The surfactant used in the production method of the present disclosure can improve the stability of the aqueous dispersion, and is more preferably used in a polymerization method in which a poorly water-soluble substance such as an initiator such as an organic peroxide or a chain transfer agent such as an iodine or bromine compound is added during the polymerization as described above.

[0423] The gum is a small granular mass of fluororubber, and the crumb is an amorphous mass formed when the fluororubber cannot maintain the small granular shape of a gum at room temperature and melts together.

[0424] The above-mentioned fluororubber can be processed into a fluororubber composition by adding a curing agent, a filler, etc.

[0425] Examples of the curing agent include polyols, polyamines, organic peroxides, organotins, bis(aminophenol)tetraamines, and bis(thioaminophenols).

[0426] The fluororubber composition is made of the above-mentioned fluororubber, and is therefore advantageous in that it contains substantially no emulsifier and is easily crosslinked during molding.

[0427] The fluororubber can be molded to obtain a fluororubber molded article. The method for the molding is not particularly limited, and examples of the method include known methods using the above-mentioned curing agents.

[0428] The above-mentioned fluororubber molded article is suitable for use as a seal, a gasket, an electric wire covering, a hose, a tube, a laminate, an accessory, etc., and is particularly suitable for use as parts for semiconductor manufacturing equipment, automobile parts, etc.

[0429] The polymerization usually results in an aqueous dispersion containing the fluoropolymer. The fluoropolymer usually has a concentration of 8 to 50 mass% in the aqueous dispersion obtained by carrying out the polymerization. In the aqueous dispersion, the preferred lower limit of the fluoropolymer concentration is 10 mass%, more preferably 15 mass%, and the preferred upper limit is 40 mass%, more preferably 35 mass%.

[0430] The aqueous dispersion obtained by carrying out the above polymerization may be concentrated or subjected to a dispersion stabilization treatment to form a dispersion, or may be subjected to coagulation or aggregation, recovered, and dried to form a powder or other solid matter.

[0431] The above polymer (1) can also be suitably used as a dispersant for dispersing the fluoropolymer obtained by polymerization in an aqueous medium.

[0432] In the above polymerization, an aqueous dispersion containing particles of the above fluoropolymer, the above polymer (1), and the above aqueous medium is usually obtained. The above aqueous dispersion is one in which particles of the fluoropolymer are dispersed in an aqueous medium in the presence of the above surfactant.

[0433] The polymer (1) is preferably present in an amount of 0.0001 to 15% by mass relative to the aqueous dispersion. If the amount is less than 0.0001% by mass, the dispersion stability may be poor, and if the amount is more than 15% by mass, the dispersion effect is not commensurate with the amount present, making it impractical. The lower limit of the surfactant is more preferably 0.001% by mass, the upper limit is more preferably 10% by mass, and the further upper limit is preferably 2% by mass.

[0434] The aqueous dispersion may be any one of an aqueous dispersion obtained by carrying out the above-mentioned polymerization, a dispersion obtained by concentrating this aqueous dispersion or subjecting it to a dispersion stabilization treatment, and a dispersion obtained by dispersing a powder of a fluoropolymer in an aqueous medium in the presence of the above-mentioned polymer (1).

[0435] As a method for producing the aqueous dispersion, the aqueous dispersion obtained by the polymerization can be contacted with an anion exchange resin or a mixed bed containing an anion exchange resin and a cation exchange resin in the presence of a nonionic surfactant (I), and / or (II) concentrated to a solid content concentration of 30 to 70 mass% relative to 100 mass% of the aqueous dispersion (II) to produce a purified aqueous dispersion. The nonionic surfactant is not particularly limited, but the one described below can be used. The anion exchange resin is not particularly limited, but a known one can be used. In addition, the method for contacting with the anion exchange resin can be a known method. As a method for producing the aqueous dispersion, the aqueous dispersion obtained by the polymerization is subjected to step (I), and the aqueous dispersion obtained in step (I) is subjected to step (II) to produce a purified aqueous dispersion. Alternatively, the purified aqueous dispersion can be produced by performing step (II) without performing step (I). Steps (I) and (II) can be performed repeatedly or in combination.

[0436] The anion exchange resin may, for example, have a functional group of -N + X - A strongly basic anion exchange resin having (CH3)3 groups (X represents Cl or OH), -N + X - Examples of the resin include well-known strong basic anion exchange resins having a (CH3)3(C2H4OH) group (X is the same as above). Specific examples include those described in WO 99 / 062858, WO 03 / 020836, WO 2004 / 078836, WO 2013 / 027850, and WO 2014 / 084399.

[0437] The cation exchange resin is not particularly limited, and may be, for example, a resin having a functional group of -SO3 - Strongly acidic cation exchange resin with -COO functional group - Examples of the cation exchange resin include well-known weakly acidic cation exchange resins having a cation group, etc. Among them, from the viewpoint of removal efficiency, strongly acidic cation exchange resins are preferred, and H + Strongly acidic cation exchange resins of the type are more preferred.

[0438] The above-mentioned "mixed bed consisting of a cation exchange resin and an anion exchange resin" is not particularly limited, and includes a case in which both are packed in the same column, a case in which both are packed in different columns, a case in which both are dispersed in an aqueous dispersion, etc.

[0439] The concentration method may be a known method, specifically, those described in WO 2007 / 046482 and WO 2014 / 084399. Examples of the method include phase separation, centrifugal sedimentation, cloud point concentration, electric concentration, electrophoresis, filtration using a reverse osmosis membrane (RO membrane), nanofiltration, etc. The concentration can be adjusted to a fluoropolymer concentration of 30 to 70% by mass depending on the application. The stability of the dispersion may be impaired by concentration, in which case a dispersion stabilizer may be further added. As the dispersion stabilizer, the polymer (1), the nonionic surfactant, or various other surfactants may be added. As the nonionic surfactant, the same nonionic surfactant as the nonionic surfactant exemplified as the nucleating agent described above can be appropriately used. The cloud point of a nonionic surfactant is a measure of the solubility of the surfactant in water. The surfactant used in the aqueous dispersion has a cloud point of about 30°C to about 90°C, preferably about 35°C to about 85°C.

[0440] The total amount of the dispersion stabilizer is a concentration of 0.5 to 20% by mass based on the solid content of the dispersion. If it is less than 0.5% by mass, the dispersion stability may be poor, and if it exceeds 20% by mass, the dispersion effect is not commensurate with the amount present, making it impractical. The more preferred lower limit of the dispersion stabilizer is 2% by mass, and the more preferred upper limit is 12% by mass.

[0441] The polymer (1) may be removed by the above concentration operation.

[0442] The aqueous dispersion obtained by carrying out the above polymerization can also be prepared into an aqueous dispersion having a long pot life by subjecting it to a dispersion stabilization treatment without being concentrated depending on the application. The dispersion stabilizer used can be the same as those mentioned above.

[0443] The use of the aqueous dispersion is not particularly limited, and examples of applications of the aqueous dispersion as it is include coating, which involves applying the aqueous dispersion as it is onto a substrate, drying, and optionally firing; impregnation, which involves impregnating a porous support such as a nonwoven fabric or a resin molded product, drying, and preferably firing; and cast film formation, which involves applying the aqueous dispersion onto a substrate such as glass, drying, and optionally immersing the substrate in water and peeling off the substrate to obtain a thin film. Examples of these applications include aqueous dispersion-type paints, tent films, conveyor belts, printed circuit boards (CCL), electrode binders, and electrode water repellents.

[0444] The above aqueous dispersion can be used as an aqueous coating material by blending known additives such as pigments, thickeners, dispersants, defoamers, antifreeze agents, film-forming assistants, etc., or by further combining with other polymer compounds. As additive applications, it can be used as a binding agent to prevent the active material of an electrode from falling off, as a binder, as a compound such as an anti-drip agent, and as a dust suppression treatment to prevent the scattering of soil, sand, dust, etc.

[0445] An anionic surfactant may be preferably contained for the purpose of adjusting the viscosity of the aqueous dispersion or for the purpose of improving the miscibility of pigments, fillers, etc. The anionic surfactant may be appropriately added within a range that does not cause problems in terms of economy or the environment.

[0446] The anionic surfactant may be a non-fluorinated anionic surfactant or a fluorine-containing anionic surfactant, with a non-fluorinated anionic surfactant not containing fluorine, that is, a hydrocarbon anionic surfactant being preferred.

[0447] For the purpose of adjusting the viscosity, the type of anionic surfactant is not particularly limited as long as it is a known anionic surfactant, and for example, anionic surfactants described in International Publication No. 2013 / 146950 and International Publication No. 2013 / 146947 can be used. For example, anionic surfactants having a saturated or unsaturated aliphatic chain with 6 to 40 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 9 to 13 carbon atoms can be used. The saturated or unsaturated aliphatic chain may be either a straight chain or a branched chain, or may have a cyclic structure. The hydrocarbon may be aromatic or may have an aromatic group. The hydrocarbon may have a heteroatom such as oxygen, nitrogen, or sulfur. Examples of anionic surfactants include alkyl sulfonates, alkyl sulfates, alkylaryl sulfates, and salts thereof; aliphatic (carboxylic) acids and salts thereof; alkyl phosphates, alkylaryl phosphates, and salts thereof; and among these, alkyl sulfonates, alkyl sulfates, aliphatic carboxylic acids, and salts thereof are preferred. As the alkyl sulfate or its salt, ammonium lauryl sulfate, sodium lauryl sulfate, or the like is preferred. As the aliphatic carboxylic acid or a salt thereof, succinic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric acid, hydrododecanoic acid, or a salt thereof is preferred.

[0448] The amount of the anionic surfactant added varies depending on the type of the anionic surfactant and other compounding ingredients, but is preferably 10 ppm to 5000 ppm based on the solid content mass of the fluoropolymer. The lower limit of the amount of the anionic surfactant added is more preferably 50 ppm or more, and even more preferably 100 ppm or more. If the amount added is too small, the viscosity adjusting effect is poor. The upper limit of the amount of the anionic surfactant added is more preferably 3000 ppm or less, and even more preferably 2000 ppm or less. If the amount added is too large, the mechanical stability and storage stability of the aqueous dispersion may be impaired.

[0449] For the purpose of adjusting the viscosity of the above-mentioned aqueous dispersion, in addition to the anionic surfactant, for example, methyl cellulose, alumina sol, polyvinyl alcohol, carboxylated vinyl polymer, etc. can also be blended. For the purpose of adjusting the pH of the above aqueous dispersion, a pH adjuster such as aqueous ammonia may be added.

[0450] The above aqueous dispersion may contain other water-soluble polymer compounds as required, provided that the characteristics of the aqueous dispersion are not impaired. The other water-soluble polymer compounds are not particularly limited, and examples thereof include polyethylene oxide (dispersion stabilizer), polyethylene glycol (dispersion stabilizer), polyvinylpyrrolidone (dispersion stabilizer), phenol resin, urea resin, epoxy resin, melamine resin, polyester resin, polyether resin, acrylic silicone resin, silicone resin, silicone polyester resin, polyurethane resin, etc. Furthermore, preservatives such as isothiazolone, azole, pronopol, chlorothalonil, methylsulfonyltetrachloropyrrolidone, carbentazim, fluorophorbet, sodium diacetate, and diiodomethyl-paratolylsulfone may be contained.

[0451] The polymer (1), decomposition products and by-products of the polymer (1) produced as by-products from the polymer (1), residual monomers, etc. may be recovered and purified from the wastewater generated by the coagulation or washing and / or the off-gas generated in the drying step, so that the polymer (1), decomposition products and by-products of the polymer (1) produced as by-products from the polymer (1), residual monomers, etc. may be reused. The method for the recovery and purification is not particularly limited, and may be a known method. For example, the method described in JP-A-2011-520020 may be used.

[0452] The method for recovering and purifying the polymer (1), decomposition products and by-products of the polymer (1) produced as by-products from the polymer (1), residual monomers, etc. from the wastewater generated by the coagulation, the wastewater generated by washing, and the off-gas generated in the drying step is not particularly limited, and any conventionally known method can be used, such as those described in U.S. Patent Application Publication No. 2007 / 0015937, U.S. Patent Application Publication No. 2007 / 0025902, and U.S. Patent Application Publication No. 2007 / 0027251. Specifically, the following method can be used.

[0453] Methods for recovering the polymer (1), decomposition products and by-products of the polymer (1) produced as by-products from the polymer (1), residual monomers, etc., from the wastewater include a method in which the wastewater is brought into contact with adsorption particles such as ion exchange resins, activated carbon, silica gel, clay, zeolite, etc. to adsorb the polymer (1), etc., and then the wastewater is separated from the adsorption particles. Incineration of the adsorption particles that have adsorbed the polymer (1), etc., can prevent the release of the polymer (1), etc., into the environment.

[0454] Alternatively, the polymer (1) and the like can be recovered by desorbing and eluting the polymer (1) and the like from ion exchange resin particles adsorbing the polymer (1) and the like by a known method. For example, when the ion exchange resin particles are anion exchange resin particles, the polymer (1) and the like can be eluted by contacting a mineral acid with the anion exchange resin. When a water-soluble organic solvent is subsequently added to the resulting eluate, the eluate is usually separated into two phases, and the lower phase containing the polymer (1) and the like is recovered and neutralized, whereby the polymer (1) and the like can be recovered. Examples of the water-soluble organic solvent include polar solvents such as alcohols, ketones, and ethers.

[0455] Other methods for recovering the polymer (1) from the ion-exchange resin particles include a method using an ammonium salt and a water-soluble organic solvent, and a method using an alcohol and, if desired, an acid. In the latter method, an ester derivative of the polymer (1) is produced, which can be easily separated from the alcohol by distillation.

[0456] When the wastewater contains fluoropolymer particles and other solids, it is preferable to remove them before contacting the wastewater with the adsorbent particles. Methods for removing the fluoropolymer particles and other solids include a method of precipitating them by adding aluminum salts or the like, and then separating the wastewater from the precipitate, and an electrocoagulation method. Mechanical methods may also be used for removal, such as cross-flow filtration, deep bed filtration, and precoat filtration. The concentration of the unagglomerated fluoropolymer in the wastewater is preferably low from the viewpoint of productivity, more preferably less than 0.4 mass %, particularly preferably less than 0.3 mass %.

[0457] As a method for recovering the polymer (1) and the like from the off-gas, there can be mentioned a method in which a scrubber is used to contact the off-gas with deionized water, an aqueous alkali solution, an organic solvent such as a glycol ether solvent, etc., to obtain a scrubber solution containing a surfactant and the like. When a high-concentration aqueous alkali solution is used as the aqueous alkali solution, the scrubber solution can be recovered in a state in which the polymer (1) and the like are phase-separated, so that the recovery and reuse of the polymer (1) and the like can be easily achieved. Examples of the alkaline compound include alkali metal hydroxides and quaternary ammonium salts.

[0458] The scrubber solution containing the polymer (1) etc. may be concentrated using a reverse osmosis membrane or the like. The concentrated scrubber solution usually contains fluorine ions, but by further adding alumina after concentration to remove the fluorine ions, it is possible to facilitate the reuse of the polymer (1) etc. Alternatively, the scrubber solution may be brought into contact with adsorbent particles to adsorb the polymer (1) etc., and the polymer (1) etc. may be recovered by the above-mentioned method.

[0459] The polymer (1) etc. recovered by any of the above methods can be reused in the production of fluoropolymers.

[0460] The present disclosure also relates to a use of a polymer for producing a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium, characterized in that the polymer is a polymer (1) comprising polymerization units (1) based on a monomer represented by the following general formula (1). CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom. The aqueous medium, the fluoromonomer, and the fluoropolymer are preferably the same as those that can be used in the production method of the present disclosure. The preferred configuration of the polymer (1) is the same as that of the polymer (1) used in the production method of the present disclosure.

[0461] The present disclosure also relates to a composition comprising a fluoropolymer and a polymer (1) containing polymerized units (1) based on a monomer represented by the following general formula (1): CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 74. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom. In the composition of the present disclosure, the polymerized units (1) are preferably polymerized units (1A) based on a monomer represented by the following general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)

[0462] The fluoropolymer may be any fluoropolymer different from the polymer (1), and is preferably the same as that which can be used in the production method of the present disclosure, and is more preferably a fluororesin, and among these, the above-mentioned fluororesin having a fluorine substitution rate of 50% or more is even more preferable, the above-mentioned fluororesin having a fluorine substitution rate of more than 50% is even more preferable, the above-mentioned fluororesin having a fluorine substitution rate of 55% or more is even more preferable, the above-mentioned fluororesin having a fluorine substitution rate of 60% or more is even more preferable, the above-mentioned fluororesin having a fluorine substitution rate of 75% or more is even more preferable, the above-mentioned fluororesin having a fluorine substitution rate of 80% or more is particularly preferable, and the above-mentioned fluororesin having a fluorine substitution rate of 90 to 100%, i.e., a perfluororesin, is most preferable.

[0463] As the perfluororesin, a fluororesin having a fluorine substitution rate of 95 to 100% is more preferable, PTFE, FEP, and PFA are further preferable, and PTFE is particularly preferable. That is, in the above composition, the fluoropolymer is preferably polytetrafluoroethylene. Moreover, from the viewpoints of the stability and yield of the aqueous dispersion, the above PTFE is more preferably modified PTFE.

[0464] The preferred configuration of the polymer (1) is the same as that of the polymer (1) used in the production method of the present disclosure.

[0465] One embodiment of the composition of the present disclosure may be an aqueous dispersion, a powder, or a pellet. The aqueous dispersion may be a dispersion after polymerization, or may be a dispersion processed after polymerization. For example, a nonionic surfactant may be added for mechanical stability or storage stability. When the nonionic surfactant is added, the amount of the nonionic surfactant added is preferably 0.5 to 25% by mass relative to the fluoropolymer. A more preferred lower limit is 1% by mass, an even more preferred lower limit is 3% by mass, a more preferred upper limit is 20% by mass, an even more preferred upper limit is 15% by mass, and an even more preferred upper limit is 10% by mass.

[0466] The aqueous dispersion is a dispersion system in which an aqueous medium is used as a dispersion medium and the fluoropolymer is used as a dispersoid. The aqueous medium is not particularly limited as long as it is a liquid containing water, and may contain, in addition to water, an organic solvent such as alcohol, ether, ketone, or paraffin wax.

[0467] The lower limit of the content of the polymer (1) in the composition is preferably 0.0001% by mass, more preferably 0.001% by mass, even more preferably 0.01% by mass, and particularly preferably 0.1% by mass, based on the fluoropolymer. The upper limit is preferably 20% by mass, more preferably 10% by mass, even more preferably 6% by mass, even more preferably 4% by mass, particularly preferably 2% by mass or less, particularly preferably 1.5% by mass or less, and most preferably 1% by mass or less. In this specification, the content of the polymer (1) is determined by solid-state NMR measurement. Methods for measuring the content of the polymer (1) include those described in WO 2014 / 099453, WO 2010 / 075497, WO 2010 / 075496, WO 2011 / 008381, WO 2009 / 055521, WO 1987 / 007619, JP 61-293476 A, WO 2010 / 075494, WO 2010 / 075359, WO 2012 / 082454, WO 2006 / 119224, WO 2013 / 085864, and JP 2014 / 092266. Measurement methods for each of the polymers described in International Publication No. 2012 / 082707, International Publication No. 2012 / 082703, International Publication No. 2012 / 082454, International Publication No. 2012 / 082451, International Publication No. 2006 / 135825, International Publication No. 2004 / 067588, International Publication No. 2009 / 068528, JP 2004-075978 A, JP 2001-226436 A, International Publication No. 1992 / 017635, International Publication No. 2014 / 069165, JP 11-181009 A and the like are described. The content of the polymer (1) in the composition may be, for example, 19 It can be determined by F-MAS NMR measurement. Specific examples of devices that can be used include AVANCE III HD400 manufactured by Bruker Corporation and AVANCE300 manufactured by Bruker Corporation. The rotation speed is set according to the resonance frequency of the apparatus so that the spinning side bands do not overlap with the peaks used to calculate the contents of the fluoropolymer and the polymer (1).

[0468] The present disclosure also relates to a molded article made of the composition. The molded article is preferably a stretched article, and examples of the stretched article include, but are not limited to, threads, tubes, tapes, films (uniaxially stretched films, biaxially stretched films), etc.

[0469] In the composition of the present disclosure, the fluoropolymer is preferably polytetrafluoroethylene. The composition of the present disclosure will be described in more detail below with respect to the case where the fluoropolymer is polytetrafluoroethylene.

[0470] The composition of the present disclosure is a composition containing polytetrafluoroethylene and polymer (1). The content of polymer (1) is preferably 0.0001% by mass or more and 20% by mass or less based on polytetrafluoroethylene. In the composition of the present disclosure, the lower limit of the content of polymer (1) is more preferably 0.001% by mass, even more preferably 0.01% by mass, and particularly preferably 0.1% by mass, based on polytetrafluoroethylene. The upper limit is more preferably 10% by mass, even more preferably 6% by mass, even more preferably 4% by mass, especially preferably 2% by mass or less, particularly preferably 1.5% by mass or less, and most preferably 1% by mass or less. The content of the polymer (1) can be determined by solid-state NMR measurement. For example, in the above composition, when polymer (1) is a copolymer of TFE and a monomer represented by CH2=CF(CF2OCFCF3COONH4), when determining the content of the copolymer of TFE and a monomer represented by CH2=CF(CF2OCFCF3COONH4) in the composition, the rotation speed may be set to 30 kHz when using AVANCE300 manufactured by Bruker Japan Ltd. For example, in the above composition, when the polymer (1) is a copolymer of TFE and a monomer represented by CH2=CF(CF2OCFCF3COONH4), the content of the copolymer of TFE and a monomer represented by CH2=CF(CF2OCFCF3COONH4) in the composition is 19 It can be calculated using the following formula from the spectrum obtained by F-MAS NMR measurement (rotation speed: 30 kHz). Y = (400B / (5xA+3xB)) x 100 Y: Content (mol%) of copolymer of TFE and monomer represented by CH2=CF(CF2OCFCF3COONH4) A: -120ppm signal integral B: Sum of integrals of CF2 and CF3 signals at -83 ppm The chemical shift value was determined by setting the peak top of the signal derived from the main chain of PTFE at −120 ppm. x: The proportion (mol%) of polymerization units based on the monomer represented by CH2=CF(CF2OCFCF3COONH4) in the copolymer of TFE and the monomer represented by CH2=CF(CF2OCFCF3COONH4)

[0471] In the composition of the present disclosure, the total amount of polytetrafluoroethylene and polymer (1) is preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably substantially 100% by mass.

[0472] In the compositions of the present disclosure, the polytetrafluoroethylene is more preferably a modified polytetrafluoroethylene.

[0473] The aspect ratio of the primary particle of the polytetrafluoroethylene is preferably less than 2.00, more preferably 1.90 or less, even more preferably 1.80 or less, even more preferably 1.70 or less, especially preferably 1.60 or less, and particularly preferably 1.50 or less. The aspect ratio is more preferably 1.45 or less, even more preferably 1.40 or less, even more preferably 1.35 or less, especially preferably 1.30 or less, particularly preferably 1.20 or less, and most preferably 1.10 or less. When measuring in an aqueous dispersion, the above aspect ratio is determined by observing an aqueous PTFE dispersion diluted to a solids concentration of approximately 1% by mass with a scanning electron microscope (SEM), processing the images of 400 or more particles randomly selected, and averaging the ratio of the long axis to the short axis. When measuring the aspect ratio in powder form, the PTFE powder is irradiated with an electron beam, then added to an aqueous fluorosurfactant solution, and redispersed by ultrasonic waves to obtain an aqueous PTFE dispersion. The aspect ratio is determined from this aqueous PTFE dispersion in the same manner as in the aqueous dispersion.

[0474] The composition of the present disclosure can also be suitably used as a material for forming a stretched body (stretching material). That is, the composition of the present disclosure is preferably stretchable. The composition of the present disclosure preferably has a content of polymer (1) of 0.0001% by mass or more and 20% by mass or less based on polytetrafluoroethylene, and is stretchable. When used as a stretching material, the composition of the present disclosure is preferably in the form of a powder. In this specification, "stretchable" is determined according to the following criteria. 21.7 g of lubricant (trade name: Isopar H (registered trademark), Exxon) is added to 100 g of PTFE powder and mixed in a glass bottle at room temperature for 3 minutes. The glass bottle is then left at room temperature (25°C) for at least 1 hour before extrusion to obtain a lubricated resin. The lubricated resin is paste extruded at room temperature through an orifice (diameter 2.5 mm, land length 11 mm, introduction angle 30°) at a reduction ratio of 100:1 to obtain a uniform bead. The extrusion speed, i.e., ram speed, is 20 in / min (51 cm / min). The bead obtained by paste extrusion is heated at 230°C for 30 minutes to remove the lubricant from the bead. The bead (extrusion molded body) is then cut to an appropriate length, clamped at each end so that the clamp distance is 1.5 in (38 mm), and heated to 300°C in an air circulating oven. The clamps are then separated at a desired speed (stretch rate) until a separation distance corresponding to the desired stretch (total stretch) is achieved, and a stretch test is performed. The stretch method essentially follows that disclosed in U.S. Pat. No. 4,576,869, except for the difference in extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" is the increase in length due to stretching, and is usually expressed relative to the original length. In the above preparation, the stretch rate is 1000% / sec, and the total stretch is 2400%. This means that the stretch test results in a stretched bead with a uniform appearance without breakage.

[0475] The composition of the present disclosure preferably has a standard specific gravity (SSG) of 2.200 or less. By having a standard specific gravity of 2.200 or less, it is possible to obtain a composition that can be stretched, and also to obtain a stretched product having excellent breaking strength. The standard specific gravity is preferably 2.195 or less, more preferably 2.190 or less, and even more preferably 2.185 or less. The standard specific gravity is measured by a water displacement method according to ASTM D-792 using a sample molded in accordance with ASTM D4895-89.

[0476] The composition of the present disclosure has an extrusion pressure of preferably 30.0 MPa or less, more preferably 25.0 MPa or less, preferably 5.0 MPa or more, and more preferably 10.0 MPa or more. The extrusion pressure is a value determined by the following method according to the method described in JP 2002-201217 A. 21.7 g of lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon Corp.) is added to 100 g of PTFE powder and mixed in a glass bottle at room temperature for 3 minutes. The glass bottle is then left at room temperature (25°C) for at least 1 hour before extrusion to obtain a lubricated resin. The lubricated resin is paste-extruded at room temperature through an orifice (diameter 2.5 mm, land length 11 mm, introduction angle 30°) at a reduction ratio of 100:1 to obtain a uniform bead (extrusion molded body). The extrusion speed, i.e., the ram speed, is 20 inches / min (51 cm / min). The extrusion pressure is the load measured when the extrusion load reaches equilibrium in the paste extrusion and divided by the cross-sectional area of ​​the cylinder used for the paste extrusion.

[0477] The composition of the present disclosure preferably has a breaking strength of 10.0 N or more. The composition of the present disclosure preferably has a polymer (1) content of 0.0001 mass % or more and 20 mass % or less relative to polytetrafluoroethylene, and has a breaking strength of 10.0 N or more.

[0478] The breaking strength is more preferably 13.0 N or more, even more preferably 16.0 N or more, and even more preferably 19.0 N or more. The higher the breaking strength, the better, but the upper limit of the breaking strength is, for example, 50.0 N. The breaking strength is a value determined by the following method. First, an extrusion bead stretching test is carried out by the following method to prepare a sample for measuring breaking strength. The bead obtained by the above paste extrusion is heated at 230°C for 30 minutes to remove the lubricant from the bead. The bead (extrudate) is then cut to the appropriate length, clamped at each end with a clamp distance of 1.5 inches (38 mm) between the clamps, and heated to 300°C in an air circulating oven. The clamps are then moved apart at a desired speed (stretch rate) until a separation distance corresponding to the desired stretch (total stretch) is achieved, and a stretch test is performed. This stretching method essentially follows the method disclosed in U.S. Pat. No. 4,576,869, except for the extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" is the increase in length due to drawing, and is usually expressed in relation to the original length. In the above preparation method, the stretch rate is 1000% / sec and the total stretch is 2400%. The stretched bead (produced by stretching the bead) obtained in the above stretching test is clamped and fixed in a movable jaw having a gauge length of 5.0 cm, and a tensile test is performed at 25°C and a speed of 300 mm / min. The strength at which it breaks is taken as the breaking strength.

[0479] The composition of the present disclosure preferably has a stress relaxation time of 50 seconds or more, more preferably 80 seconds or more, even more preferably 100 seconds or more, and may be 150 seconds or more. The above stress relaxation time is a value measured by the following method. Both ends of the stretched bead obtained from the stretch test above are attached to a fixture to produce a taut bead sample with a total length of 8 inches (20 cm). The oven is maintained at 390°C and the fixture is inserted into the oven through a (covered) slit in the side of the oven. The time it takes for the bead sample to break from the point of insertion into the oven is the stress relaxation time.

[0480] The composition of the present disclosure is preferably substantially free of fluorine-containing surfactant. In this specification, "substantially free of fluorine-containing surfactant" means that the fluorine-containing surfactant is 10 ppm or less relative to the fluoropolymer. The content of the fluorine-containing surfactant is preferably 1 ppm or less, more preferably 100 ppb or less, even more preferably 10 ppb or less, and even more preferably 1 ppb or less, and particularly preferably the fluorine-containing surfactant is below the detection limit as measured by liquid chromatography-mass spectrometry (LC / MS / MS). The amount of the fluorine-containing surfactant can be quantified by a known method. For example, it can be quantified by LC / MS / MS analysis. First, the obtained aqueous dispersion, powder, molded body, pellet, or fluoropolymer obtained by pulverizing the molded body, or fluoropolymer obtained by pulverizing the pellet is extracted in an organic solvent such as methanol, and the molecular weight information of the extract is extracted from the LC / MS / MS spectrum, and the agreement with the structural formula of the candidate surfactant is confirmed. The identified surfactant is then prepared in aqueous solutions at five or more levels of concentration, and LC / MS / MS analysis is performed for each concentration to create a calibration curve with respect to the area. The obtained aqueous dispersion, powder, or powder obtained by pulverizing the molded body is subjected to Soxhlet extraction with methanol, and the extract can be quantitatively measured by LC / MS / MS analysis. The fluorine-containing surfactant is the same as that exemplified in the production method of the present disclosure described above. For example, it may be a surfactant containing fluorine atoms whose total carbon number excluding the anionic group is 20 or less, a surfactant containing fluorine whose anionic moiety has a molecular weight of 800 or less, and a fluorine-containing surfactant whose LogPOW is 3.5 or less. The anionic fluorine-containing surfactant may be a surfactant represented by the general formula (N 0 ) is exemplified. Specifically, the compound represented by the general formula (N 1 ), a compound represented by the general formula (N 2 ), a compound represented by the general formula (N 3 ), a compound represented by the general formula (N 4 ) and a compound represented by the general formula (N 5 ) represented by the compound represented by the formula (I). More specifically, perfluorocarboxylic acid (I) represented by the general formula (I), ω-H perfluorocarboxylic acid (II) represented by the general formula (II), perfluoropolyether carboxylic acid (III) represented by the general formula (III), perfluoroalkyl alkylene carboxylic acid (IV) represented by the general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by the general formula (V), perfluoroalkyl sulfonic acid (VI) represented by the general formula (VII), ω-H perfluoro sulfonic acid (VII) represented by the general formula (VII), perfluoroalkyl alkylene sulfonic acid (VIII) represented by the general formula (VIII), alkyl alkylene carboxylic acid (IX) represented by the general formula (IX), fluorocarboxylic acid (X) represented by the general formula (X), alkoxy fluoro sulfonic acid (XI) represented by the general formula (XI), and compound (XII) represented by the general formula (XII) are listed.

[0481] The present disclosure also provides an extruded body obtained by extruding the above composition. The extrusion may be performed by any conventionally known method and under any conditions for extruding PTFE, and is not limited thereto.

[0482] The present disclosure further provides an elongated body comprising a polymer (1) including polytetrafluoroethylene and polymerization units (1) based on a monomer represented by the following general formula (1), and having a breaking strength of 10.0 N or more: CX2=CY(-CZ2-O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond; A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom.

[0483] In the stretched body of the present disclosure, the polytetrafluoroethylene and the polymer (1) are the same as those described for the composition of the present disclosure, and suitable embodiments of each can be adopted.

[0484] The stretched body of the present disclosure preferably has a breaking strength of 13.0 N or more, more preferably 16.0 N or more, and even more preferably 19.0 N or more. The higher the breaking strength, the better, but the upper limit of the breaking strength is, for example, 50.0 N. The breaking strength of the stretched body is measured by clamping and fixing the stretched body between movable jaws having a gauge length of 5.0 cm, and conducting a tensile test at 25° C. and a speed of 300 mm / min., and the strength at which the stretched body breaks is taken as the breaking strength.

[0485] The stretched body of the present disclosure preferably has a stress relaxation time of 50 seconds or more, more preferably 80 seconds or more, even more preferably 100 seconds or more, and may be 150 seconds or more. The stress relaxation time is a value measured by the following method. The stress relaxation time of the above-mentioned stretched specimen is measured by attaching both ends of the stretched specimen to fixtures to create a taut sample of 8 inches (20 cm) in length, holding the specimen at 390°C in an oven and inserting the fixtures into the oven through a (covered) slit in the side of the oven. The time required for the sample to break from the time of insertion into the oven is the stress relaxation time.

[0486] The stretched product of the present disclosure preferably has an endothermic peak temperature between 325 and 350° C. In addition, the stretched product of the present disclosure preferably has an endothermic peak temperature between 325 and 350° C. and between 360 and 390° C. The endothermic peak temperature is a temperature corresponding to a maximum value in a heat of fusion curve when the stretched product is heated at a rate of 10° C. / min using a differential scanning calorimeter [DSC].

[0487] The stretched body of the present disclosure preferably has a porosity in the range of 30% to 99%. The porosity is more preferably 40% or more, even more preferably 50% or more, even more preferably 60% or more, and particularly preferably 70% or more. If the proportion of PTFE in the stretched body is too small, the strength of the stretched body may be insufficient, so the porosity is preferably 95% or less, and more preferably 90% or less. The porosity of the stretched body can be calculated from the apparent density ρ according to the following formula. Porosity (%)=[(2.2-ρ) / 2.2]×100 In the above formula, 2.2 is the true density of PTFE (g / cm 3 ). When the stretched body is in the form of a film or sheet, the mass of a sample cut to a specific size is measured using a precision balance, and the density of the sample is calculated from the measured mass and film thickness using the following formula. ρ=M / (4.0×12.0×t) ρ=density (film density) (g / cm3) M=mass (g) t = film thickness (cm) The above measurements and calculations are carried out at three locations, and the average value is taken as the film density. The film thickness is measured by using a film thickness meter to measure the total film thickness of five stacked stretched bodies, and dividing the measured value by five to obtain the film thickness of one sheet. When the elongated body is cylindrical, the density ρ of the elongated body is determined by measuring the mass of a sample cut to a certain length using a precision balance, and calculating the density of the sample from the measured mass and outer diameter of the sample using the following formula. ρ=M / (r×r×π)×L ρ=density (g / cm3) M=mass (g) r=radius (cm) L=Length(cm) π=pi The outer diameter of the elongated body is measured using a laser displacement sensor, and the radius is calculated by dividing the outer diameter by two. The above measurements and calculations are carried out at three locations, and the average value is taken as the density.

[0488] In the stretched product of the present disclosure, the content of polymer (1) is preferably 0.0001% by mass or more and 20% by mass or less based on polytetrafluoroethylene. In the stretched product of the present disclosure, the lower limit of the content of polymer (1) is more preferably 0.001% by mass, even more preferably 0.01% by mass, and particularly preferably 0.1% by mass, based on polytetrafluoroethylene. The upper limit is more preferably 10% by mass, even more preferably 6% by mass, even more preferably 4% by mass, especially preferably 2% by mass or less, particularly preferably 1.5% by mass or less, and most preferably 1% by mass or less. The content of the polymer (1) can be determined by solid-state NMR measurement.

[0489] The stretched body of the present disclosure is preferably substantially free of fluorine-containing surfactant. In this specification, "substantially free of fluorine-containing surfactant" means that the fluorine-containing surfactant is 10 ppm or less relative to the fluoropolymer. The content of the fluorine-containing surfactant is preferably 1 ppm or less, more preferably 100 ppb or less, even more preferably 10 ppb or less, and even more preferably 1 ppb or less, and particularly preferably the fluorine-containing surfactant is below the detection limit as measured by liquid chromatography-mass spectrometry (LC / MS / MS). The amount of the fluorine-containing surfactant can be quantified by a known method. For example, it can be quantified by LC / MS / MS analysis. First, the finely divided stretched body is extracted in an organic solvent such as methanol, and the molecular weight information of the extract is extracted from the LC / MS / MS spectrum, and a match with the structural formula of a candidate surfactant is confirmed. The identified surfactant is then prepared in aqueous solutions at five or more levels of concentration, and LC / MS / MS analysis is performed for each concentration to create a calibration curve with respect to the area. The obtained elongated body is pulverized into a powder, which is subjected to Soxhlet extraction with methanol, and the extract can be quantitatively measured by LC / MS / MS analysis. The fluorine-containing surfactant is the same as that exemplified in the production method of the present disclosure described above. For example, it may be a surfactant containing fluorine atoms whose total carbon number excluding the anionic group is 20 or less, a surfactant containing fluorine whose anionic moiety has a molecular weight of 800 or less, and a fluorine-containing surfactant whose LogPOW is 3.5 or less. The anionic fluorine-containing surfactant may be a surfactant represented by the general formula (N 0 ) is exemplified. Specifically, the compound represented by the general formula (N 1 ), a compound represented by the general formula (N 2 ), a compound represented by the general formula (N 3 ), a compound represented by the general formula (N 4 ) and a compound represented by the general formula (N 5) represented by the compound represented by the formula (I). More specifically, perfluorocarboxylic acid (I) represented by the general formula (I), ω-H perfluorocarboxylic acid (II) represented by the general formula (II), perfluoropolyether carboxylic acid (III) represented by the general formula (III), perfluoroalkyl alkylene carboxylic acid (IV) represented by the general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by the general formula (V), perfluoroalkyl sulfonic acid (VI) represented by the general formula (VII), ω-H perfluoro sulfonic acid (VII) represented by the general formula (VII), perfluoroalkyl alkylene sulfonic acid (VIII) represented by the general formula (VIII), alkyl alkylene carboxylic acid (IX) represented by the general formula (IX), fluorocarboxylic acid (X) represented by the general formula (X), alkoxy fluoro sulfonic acid (XI) represented by the general formula (XI), and compound (XII) represented by the general formula (XII) are listed.

[0490] The stretched body of the present disclosure can be obtained by stretching the composition of the present disclosure.

[0491] The elongated body of the present disclosure is also preferably in the form of a film, a tube, a fiber, or a rod.

[0492] When the stretched body of the present disclosure is a membrane (stretched membrane or porous membrane), it can be stretched by a known PTFE stretching method. Preferably, a sheet-like or rod-like paste extrudate is roll-stretched in the extrusion direction to obtain a uniaxially stretched membrane. Furthermore, a biaxially stretched film can also be obtained by stretching the film in the width direction using a tenter or the like. It is also preferable to carry out a semi-baking treatment before stretching.

[0493] The stretched body of the present disclosure is a porous body having a high porosity, and can be suitably used as a filter medium for various precision filters such as air filters and chemical liquid filters, a support material for polymer electrolyte membranes, and the like. They are also useful as materials for products used in the fields of textiles, medicine, electrochemicals, sealing materials, air filtration, ventilation / internal pressure regulation, liquid filtration, and general consumer goods. Specific applications are given below as examples.

[0494] Electrochemical Field Dielectric material prepreg, EMI shielding material, heat transfer material, etc. More specifically, printed wiring board, electromagnetic shielding material, insulating heat transfer material, insulating material, etc. Sealing materials field Gaskets, packing, pump diaphragms, pump tubes, aircraft sealing materials, etc.

[0495] Air Filtration Field ULPA filters (for semiconductor manufacturing), HEPA filters (for hospitals and semiconductor manufacturing), cylindrical cartridge filters (for industrial use), bag filters (for industrial use), heat-resistant bag filters (for exhaust gas treatment), heat-resistant pleated filters (for exhaust gas treatment), SINBRAN filters (for industrial use), catalyst filters (for exhaust gas treatment), adsorbent filters (for HDD installation), adsorbent vent filters (for HDD installation), vent filters (for HDD installation and others), vacuum cleaner filters (for vacuum cleaners), general-purpose multi-layer felt material, GT cartridge filters (for GT compatible products), cooling filters (for electronic equipment housings), etc.

[0496] Ventilation / internal pressure regulation field Freeze-drying materials such as freeze-drying containers, automotive ventilation materials for electronic circuits and lamps, container applications such as container caps, protective ventilation applications for electronic devices including small terminals such as tablet terminals and mobile phones, medical ventilation applications, etc.

[0497] Liquid Filtration Semiconductor liquid filtration filters (for semiconductor manufacturing), hydrophilic PTFE filters (for semiconductor manufacturing), chemical filters (for chemical liquid treatment), pure water production line filters (for pure water production), backwash type liquid filtration filters (for industrial wastewater treatment), etc.

[0498] General consumer goods field Clothing, cable guides (movable wires for motorcycles), motorcycle clothing, cast liners (medical supporters), vacuum cleaner filters, bagpipes (musical instruments), cables (signal cables for guitars, etc.), strings (for stringed instruments), etc.

[0499] Textiles PTFE fiber (textile material), sewing thread (textile), weaving thread (textile), rope, etc.

[0500] Medical field Internal implants (extended products), artificial blood vessels, catheters, general surgery (tissue reinforcement materials), head and neck products (dura substitutes), oral health (tissue regenerative medicine), orthopedics (bandages), etc. EXAMPLES

[0501] Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0502] The values ​​in the examples were measured by the following methods.

[0503] Average primary particle size The aqueous fluoropolymer dispersion was diluted with water until the solid content was 0.15% by mass, and the transmittance of the 550 nm projected light per unit length of the diluted latex was measured, and the number-based length average primary particle diameter was determined by measuring the unidirectional diameter using a transmission electron microscope photograph, to create a calibration curve. Using this calibration curve, the average primary particle diameter was determined from the measured transmittance of the 550 nm projected light for each sample.

[0504] Standard specific gravity (SSG) Using samples molded in accordance with ASTM D4895-89, the measurement was performed by the water displacement method in accordance with ASTM D-792.

[0505] Melting point (peak temperature) For the PTFE powder obtained in the examples, a heat of fusion curve was drawn using a differential scanning calorimeter (DSC) at a temperature rise rate of 10°C / min, and the temperature corresponding to the maximum value of the endothermic peak appearing in the heat of fusion curve was determined as the melting point of PTFE. Furthermore, for the melt-processable fluororesin (PFA, FEP) powder obtained in the examples, a differential scanning calorimeter (DSC) was used to draw a heat of fusion curve when the powder was heated to above the melting point at a heating rate of 10°C / min, cooled to below the melting point at a heating rate of 10°C / min, and then heated again to above the melting point at a heating rate of 10°C / min. The temperature corresponding to the maximum value of the endothermic peak appearing in the heat of fusion curve was determined as the melting point of the melt-processable fluororesin (PFA, FEP).

[0506] Modified Monomer Content The HFP content was determined by press-molding PTFE powder to create a thin-film disk, and the infrared absorbance of the thin-film disk was measured by FT-IR. -1 Absorbance at / 935cm -1 The absorbance ratio was calculated by multiplying the absorbance ratio at PMVE content is solid 19 The formula below was used to calculate the F-MAS NMR spectrum (30 kHz). X = (4B / 3) / (A+(B / 3)) x 100 X:PMVE content (mol%) A: -120ppm signal integral B: Integrated value of the CF signal at -52 ppm The chemical shift value was determined by setting the peak top of the signal derived from the main chain of PTFE at −120 ppm. The content of CH2=CF(CF2OCFCF3COONH4) (hereinafter also referred to as "modified monomer a") is the total amount of modified monomer a charged.

[0507] Fluoropolymer solids concentration 1 g of the aqueous fluoropolymer dispersion is dried in a blower dryer at 150° C. for 60 minutes, and the ratio of the mass of the heating residue to the mass (1 g) of the aqueous dispersion is expressed as a percentage.

[0508] Content of polymer (1) Contents of polymers A to D in PTFE powder The contents of polymers A to D contained in the PTFE powder are 19 The formula below was used to calculate the F-MAS NMR spectrum (30 kHz). Y = (4B / (5A+3B)) x 100 Y: Content of polymers A to D (mol%) A: -120ppm signal integral B: Sum of integrals of CF2 and CF3 signals at -83 ppm The chemical shift value was determined by setting the peak top of the signal derived from the main chain of PTFE at −120 ppm.

[0509] Content of polymer E The content of polymer E in the PTFE powder is 19 The formula below was used to calculate the F-MAS NMR spectrum (30 kHz). Y = (4B / (10A+3B)) x 100 Y: Content of polymer E (mol%) A: -120ppm signal integral B: Sum of integrals of CF2 and CF3 signals at -81 and -83 ppm The chemical shift value was determined by setting the peak top of the signal derived from the main chain of PTFE at −120 ppm.

[0510] Polymer F content The content of polymer F in the PTFE powder is 19 The formula below was used to calculate the F-MAS NMR spectrum (30 kHz). Y = (4B / (4.62A+2.77B)) x 100 Y: Content of polymer F (mol%) A: -120ppm signal integral B: Sum of integrals of CF2 and CF3 signals at -83 ppm The chemical shift value was determined by setting the peak top of the signal derived from the main chain of PTFE at −120 ppm.

[0511] Extrusion pressure measurement 21.7 g of lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon Corp.) is added to 100 g of fine powder and mixed in a glass bottle at room temperature for 3 minutes. The glass bottle is then left at room temperature (25°C) for at least 1 hour before extrusion to obtain a lubricated resin. The lubricated resin is paste-extruded through an orifice (diameter 2.5 mm, land length 11 mm, introduction angle 30°) at room temperature with a reduction ratio of 100:1 to obtain a uniform bead (extrusion molded body). The extrusion speed, i.e., the ram speed, is 20 inches / min (51 cm / min). The extrusion pressure is determined by measuring the load when the extrusion load reaches equilibrium in the paste extrusion and dividing it by the cross-sectional area of ​​the cylinder used for the paste extrusion.

[0512] Extension test The bead obtained by the above paste extrusion is heated at 230°C for 30 minutes to remove the lubricant from the bead. The bead (extrudate) is then cut to the appropriate length, clamped at each end with a clamp distance of 1.5 inches (38 mm) apart, and heated to 300°C in an air circulating oven. The clamps are then separated at a desired speed (stretch rate) until a separation distance corresponding to the desired stretch (total stretch) is achieved, and a stretch test is performed. This stretching method essentially follows the method disclosed in U.S. Pat. No. 4,576,869, except for the extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" is the increase in length due to drawing, and is usually expressed in relation to the original length. In the above preparation method, the stretch rate is 1000% / sec and the total stretch is 2400%.

[0513] Breaking Strength The stretched bead (produced by stretching the bead) obtained in the above stretching test is clamped and fixed in a movable jaw having a gauge length of 5.0 cm, and a tensile test is performed at 25°C and a speed of 300 mm / min. The strength at the time of break is measured as the breaking strength.

[0514] Stress relaxation time Both ends of the stretched bead obtained from the stretch test above are attached to a fixture to produce a taut bead sample with a total length of 8 inches (20 cm). The oven is maintained at 390°C and the fixture is inserted into the oven through a (covered) slit in the side of the oven. The time it takes for the bead sample to break from the point of insertion into the oven is measured as the stress relaxation time.

[0515] Appearance of the stretched product The appearance of the stretched bead (produced by stretching the bead) obtained in the above stretching test is visually observed.

[0516] Aspect Ratio A PTFE aqueous dispersion diluted to a solids concentration of approximately 1% by mass was observed with a scanning electron microscope (SEM), and images of more than 400 randomly selected particles were processed to determine the average ratio of their major axis to their minor axis.

[0517] Melt Flow Rate Measured in accordance with ASTM D-1238 and D-2116.

[0518] Mooney Viscosity (ML1+10(100℃)) Measurement was performed at 100° C. in accordance with JIS K6300 using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

[0519] In the examples, the compound of the formula: CH2=CF(CF2OCFCF3COONH4) A homopolymer (number average molecular weight: 90,000, weight average molecular weight: 190,000) (hereinafter referred to as polymer A) of a monomer (modified monomer a) represented by the following formula was used. The number average molecular weight and weight average molecular weight were measured by gel permeation chromatography (GPC) using a GPC HLC-8020 manufactured by Tosoh Corporation and Shodex columns (one GPC KF-801, one GPC KF-802, and two GPC KF-806M connected in series) with tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min, and the molecular weight was calculated using monodisperse polystyrene as a standard.

[0520] Example 1 In a 1 L glass reactor equipped with a stirrer, 530 g of deionized water, 30 g of paraffin wax, 0.52 g of polymer A, and aqueous ammonia were added and the pH was adjusted to 9.2. The reactor contents were then heated to 70°C while being aspirated and simultaneously purged with TFE monomer to remove oxygen from the reactor. The contents were then stirred at 540 rpm. TFE monomer was added to the reactor until the pressure reached 0.73 MPaG. 2.75 mg of ammonium persulfate (APS) initiator dissolved in 20 g of deionized water was injected into the reactor to bring the reactor to a pressure of 0.83 MPaG. After the initiator was injected, a pressure drop occurred and the start of polymerization was observed. TFE monomer was added to the reactor to maintain the pressure, and polymerization was continued until about 140 g of TFE monomer had finished reacting. The reactor was then vented until the pressure in the reactor reached normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the aqueous PTFE dispersion. The solids concentration of the resulting PTFE aqueous dispersion was 20.8% by mass, and the average primary particle size was 258 nm. The obtained PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, and coagulated under high-speed stirring conditions. The coagulated wet powder was dried at 150°C for 18 hours. The SSG of the PTFE powder at this time was 2.180, and the melting point was 343.1°C.

[0521] Example 2 Polymerization was carried out in the same manner as in Example 1, except that the amount of polymer A in Example 1 was changed from 0.52 g to 0.275 g, the amount of ammonium persulfate (APS) initiator in Example 1 was changed to 2.75 mg, and 2.9 mg of CH2=CF(CF2OCFCF3COONH4) was added. The solid content of the obtained PTFE aqueous dispersion was 20.4 mass%, and the average primary particle size was 280 nm.

[0522] Example 3 Polymerization was carried out in the same manner as in Example 1, except that the amount of Polymer A was changed from 0.52 g in Example 1 to 1.10 g. The solid content concentration of the obtained PTFE aqueous dispersion was 19.3 mass %, and the average primary particle diameter was 336 nm.

[0523] Example 4 Polymer A in Example 1 was a homopolymer of a monomer represented by CH2=CF(CF2OCFCF3COONH4) (weight average molecular weight is 4.1×10 4 , number average molecular weight 1.9×10 4 ) was used as Polymer B, and polymerization was continued until the amount of wet PTFE aggregates adhering to the reactor and the stirring blade became approximately the same as in Example 1, except that the polymerization was continued until the amount of wet PTFE aggregates adhering to the reactor and the stirring blade became approximately the same as in Example 1. The solid content concentration of the obtained PTFE aqueous dispersion was 17.7 mass %, and the average primary particle size was 341 nm.

[0524] Example 5 Polymer B in Example 4 was a homopolymer of a monomer represented by CH2=CF(CF2OCFCF3COONH4) (weight average molecular weight is 2.7×10 4 , number average molecular weight 1.1×10 4 Polymerization was carried out in the same manner as in Example 4, except that polymer C was prepared by the procedure described above. The solid content of the resulting aqueous PTFE dispersion was 15.0% by mass, and the average primary particle diameter was 292 nm.

[0525] Example 6 Polymer B in Example 4 was a homopolymer of a monomer represented by CH2=CF(CF2OCFCF3COONH4) (weight average molecular weight of 1.9×10 4 , number average molecular weight 1.2×10 4Polymerization was carried out in the same manner as in Example 4, except that polymer D of (1) was used. The solid content concentration of the obtained PTFE aqueous dispersion was 12.9 mass %, and the average primary particle size was 289 nm.

[0526] Example 7 Polymerization was carried out in the same manner as in Example 1, except that 0.18 g of HFP was added in Example 1. The solid content concentration of the obtained PTFE aqueous dispersion was 21.5 mass %, and the average primary particle size was 211 nm. The polymerization conditions in each of Examples 1 to 7 and the evaluation results of the resulting PTFE aqueous dispersions are shown in Tables 1 and 2, respectively.

[0527] Example 8 0.52 g of polymer A in Example 1 was mixed with 0.55 g of a homopolymer of a monomer represented by CH2=CF(CF2OCFCF3CF2OCFCF3COONH4) (weight average molecular weight of 9.7×10 4 , number average molecular weight 3.3×10 4 Polymerization was carried out in the same manner as in Example 1, except that polymer E of (100%) was used and 0.13 g of PMVE was added. The solid content concentration of the obtained PTFE aqueous dispersion was 21.5 mass %, and the average primary particle diameter was 183 nm.

[0528] Example 9 Polymer E in Example 8 was a copolymer of TFE and a monomer represented by CH2=CF(CF2OCFCF3COONH4) (weight average molecular weight of 20.0×10 4 , number average molecular weight 5.8×10 4 Polymerization was carried out in the same manner as in Example 8, except that polymer F having a content of polymerization units CH2=CF(CF2OCFCF3COONH4) of 92.4 mol% relative to the total polymerization units was used. The solid content of the obtained PTFE aqueous dispersion was 19.6 mass%, and the average primary particle size was 350 nm. The polymerization conditions in Examples 8 and 9 and the evaluation results of the resulting PTFE aqueous dispersions are shown in Tables 1 and 2, respectively.

[0529] [Table 1]

[0530] [Table 2]

[0531] Example 10 In a 6L SUS reactor equipped with a stirrer, 3560g of deionized water, 104g of paraffin wax, 5.37g of polymer A, and 77.3mg of CH2=CF(CF2OCFCF3COONH4) were placed. Ammonia water was added to adjust the pH to 9.1. The contents of the reactor were then heated to 70°C while being aspirated and purged with TFE at the same time to remove oxygen from the reactor, and the contents were stirred. 0.8g of HFP was added to the reactor, and TFE was added until the pressure reached 0.73MPaG. 17.9mg of ammonium persulfate (APS) initiator dissolved in 20g of deionized water was injected into the reactor, and the reactor was brought to a pressure of 0.83MPaG. After the injection of the initiator, a drop in pressure occurred and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 0.78MPaG. When the amount of TFE consumed in the reaction reached about 180g, the supply of TFE and stirring were stopped. The gas in the reactor was then slowly released until the pressure in the reactor reached 0.02 MPaG. TFE was then fed until the pressure in the reactor reached 0.78 MPaG, and stirring was started again to continue the reaction. When the amount of TFE consumed in the reaction reached about 540 g, 14.3 mg of hydroquinone dissolved in 20 g of deionized water was injected into the reactor, and the reaction was continued. When the amount of TFE consumed in the reaction reached about 1250 g, the supply of TFE was stopped, stirring was stopped, and the reaction was terminated. Thereafter, the pressure in the reactor was vented until it reached normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PTFE aqueous dispersion. The solid content concentration of the obtained PTFE aqueous dispersion was 25.7 mass%, and the average primary particle size was 249 nm. The resulting PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, coagulated under high-speed stirring conditions, and the coagulated wet powder was dried at 210° C. for 18 hours. The various physical properties of the resulting PTFE powder were measured. The results are shown in Table 3.

[0532] Example 11 Polymerization was carried out in the same manner as in Example 10, except that 77.3 mg of CH2=CF(CF2OCFCF3COONH4) was changed to 9.7 mg, and 0.8 g of HFP was changed to 0.27 g of PMVE. The solid content concentration of the obtained PTFE aqueous dispersion was 24.4 mass%, and the average primary particle size was 275 nm.

[0533] Example 12 Polymerization was carried out in the same manner as in Example 10, except that 14.3 mg of hydroquinone in Example 10 was not injected into the reactor. The solid content concentration of the obtained PTFE aqueous dispersion was 25.4 mass%, and the average primary particle size was 242 nm.

[0534] Example 13 In a 3L SUS reactor equipped with a stirrer, 1800g of deionized water, 90g of paraffin wax, 2.70g of polymer A, and 38.9mg of CH2=CF(CF2OCFCF3COONH4) were placed. Ammonia water was added to adjust the pH to 9.1. The contents of the reactor were then heated to 80°C while being aspirated and purged with TFE at the same time to remove oxygen from the reactor, and the contents were stirred. 2.3g of HFP was added to the reactor, and then TFE was added until the pressure reached 1.50MPaG. 9.0mg of ammonium persulfate (APS) initiator was injected into the reactor. After the injection of the initiator, a pressure drop occurred and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 1.50MPaG. When the amount of TFE consumed in the reaction reached about 90g, the supply of TFE and stirring were stopped. The gas in the reactor was then slowly released until the pressure in the reactor reached atmospheric pressure, and the reactor was held under vacuum for another minute. TFE was then supplied until the pressure in the reactor reached 2.50 MPaG, and stirring was started again to continue the reaction. When the amount of TFE consumed in the reaction reached about 180 g, 14.4 mg of hydroquinone dissolved in 20 g of deionized water was injected into the reactor, and the reaction was continued. When the amount of TFE consumed in the reaction reached about 600 g, the supply of TFE was stopped, stirring was stopped, and the reaction was terminated. Thereafter, the reactor was vented until the pressure in the reactor reached normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PTFE aqueous dispersion. The solid content concentration of the obtained PTFE aqueous dispersion was 26.9 mass%, and the average primary particle size was 196 nm. The resulting PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, coagulated under high-speed stirring conditions, and the coagulated wet powder was dried at 210° C. for 18 hours. The various physical properties of the resulting PTFE powder were measured. The results are shown in Table 3.

[0535] [Table 3]

[0536] Example 14 In a 6L SUS reactor equipped with a stirrer, 3560g of deionized water, 104g of paraffin wax, 3.58g of polymer A, and 51.6mg of CH2=CF(CF2OCFCF3COONH4) were placed. Ammonia water was added to adjust the pH to 9.0. The contents of the reactor were then heated to 70°C while being aspirated and purged with TFE at the same time to remove oxygen from the reactor, and the contents were stirred. 0.8g of HFP was added to the reactor, and TFE was added until the pressure reached 0.73MPaG. 17.9mg of ammonium persulfate (APS) initiator dissolved in 20g of deionized water was injected into the reactor, and the reactor was brought to a pressure of 0.83MPaG. After the injection of the initiator, a drop in pressure occurred and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 0.78MPaG. When the amount of TFE consumed in the reaction reached about 180g, the supply of TFE and stirring were stopped. The gas in the reactor was then slowly released until the pressure in the reactor reached 0.02 MPaG. TFE was then fed until the pressure in the reactor reached 0.78 MPaG, and stirring was started again to continue the reaction. When the amount of TFE consumed in the reaction reached about 900 g, the feed of TFE was stopped, stirring was stopped, and the reaction was terminated. Thereafter, the pressure in the reactor was vented until it reached normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PTFE aqueous dispersion. The solid content concentration of the obtained PTFE aqueous dispersion was 20.7% by mass, and the average primary particle size was 218 nm. The obtained PTFE aqueous dispersion was diluted with deionized water to a solid content concentration of about 10% by mass, coagulated under high-speed stirring conditions, and the coagulated wet powder was dried at 210 ° C. for 18 hours. Various physical properties of the obtained PTFE powder were measured. The results are shown in Table 4.

[0537] Example 15 Polymerization was carried out in the same manner as in Example 14, except that 51.6 mg of CH2=CF(CF2OCFCF3COONH4) in Example 14 was changed to 6.4 mg, and HFP was changed to PMVE. The solid content concentration of the obtained PTFE aqueous dispersion was 20.4 mass%, and the average primary particle diameter was 227 nm.

[0538] Example 16 Polymerization was carried out in the same manner as in Example 14, except that 3.58 g of polymer A in Example 14 was changed to 5.37 g, 51.6 mg of CH2=CF(CF2OCFCF3COONH4) was changed to 430 mg, and the supply of TFE was stopped when the amount of TFE consumed in the reaction reached about 1250 g. The solid content concentration of the obtained PTFE aqueous dispersion was 26.1 mass %, and the average primary particle size was 227 nm.

[0539] Example 17 Polymerization was carried out in the same manner as in Example 14, except that the amount of CH2=CF(CF2OCFCF3COONH4) in Example 14 was changed from 51.6 mg to 6.4 mg, and 1.8 mg of polyoxyethylene (10) octylphenyl ether was added. The solid content of the obtained PTFE aqueous dispersion was 20.3 mass%, and the average primary particle size was 227 nm.

[0540] Example 18 In a 3L SUS reactor equipped with a stirrer, 1800g of deionized water, 90g of paraffin wax, 1.80g of polymer A, and 25.9mg of CH2=CF(CF2OCFCF3COONH4) were placed. Ammonia water was added to adjust the pH to 9.1. The contents of the reactor were then heated to 80°C while being aspirated and purged with TFE at the same time to remove oxygen from the reactor, and the contents were stirred. 1.26g of HFP was added to the reactor, and then TFE was added until the pressure reached 1.50MPaG. 9.0mg of ammonium persulfate (APS) initiator was injected into the reactor. After the injection of the initiator, a pressure drop occurred and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 1.50MPaG. When the amount of TFE consumed in the reaction reached about 510g, the supply of TFE was stopped, the stirring was stopped, and the reaction was terminated. Thereafter, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PTFE aqueous dispersion. The solid content of the resulting PTFE aqueous dispersion was 23.5% by mass, and the average primary particle size was 202 nm. The resulting PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, solidified under high-speed stirring conditions, and the solidified wet powder was dried at 180°C for 18 hours. Various physical properties of the resulting PTFE powder were measured. The results are shown in Table 4.

[0541] Example 19 Polymerization was carried out in the same manner as in Example 14, except that HFP was not added and the operation was not performed when the amount of TFE consumed in the reaction reached about 180 g. The solid content concentration of the obtained PTFE aqueous dispersion was 20.1 mass%, and the average primary particle size was 277 nm.

[0542] Example 20 In a 6L SUS reactor equipped with a stirrer, 3600g of deionized water, 180g of paraffin wax, 7.20g of polymer A, and 104mg of CH2=CF(CF2OCFCF3COONH4) were placed. Ammonia water was added to adjust the pH to 9.1. The contents of the reactor were then heated to 85°C while being aspirated, and simultaneously purged with TFE to remove oxygen from the reactor, and the contents were stirred. TFE was added until the pressure reached 2.70MPaG. 56mg of ammonium persulfate (APS) and 289mg of disuccinic acid peroxide (DSP) were charged as polymerization initiators. The initiator was injected into the reactor. After the initiator was injected, a pressure drop occurred and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 2.70MPaG. When the amount of TFE consumed in the reaction reached about 900g, the supply of TFE was stopped, the stirring was stopped, and the reaction was terminated. Thereafter, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PTFE aqueous dispersion. The solid content of the resulting PTFE aqueous dispersion was 21.0% by mass, and the average primary particle size was 197 nm. The resulting PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, and solidified under high-speed stirring conditions, and the solidified wet powder was dried at 180°C for 18 hours. Various physical properties of the resulting PTFE powder were measured. The results are shown in Table 4.

[0543] [Table 4]

[0544] Example 21 In a 1 L glass reactor equipped with a stirrer, 530 g of deionized water, 30 g of paraffin wax, 0.55 g of polymer A, and aqueous ammonia were added and the pH was adjusted to 9.1. The reactor contents were then heated to 70°C while being aspirated and simultaneously purged with TFE monomer to remove oxygen from the reactor. The contents were then stirred at 540 rpm. 0.02 g of ethane gas and 8.8 g of PPVE were added to the reactor, and then TFE monomer was added until the pressure reached 0.73 MPaG. 55 mg of ammonium persulfate (APS) initiator dissolved in 20 g of deionized water was injected into the reactor, bringing the reactor to a pressure of 0.83 MPaG. After the initiator was injected, a pressure drop occurred and the start of polymerization was observed. TFE monomer was added to the reactor to keep the pressure constant at 0.78 MPaG. Polymerization was continued until about 140 g of TFE monomer had reacted. After that, the pressure in the reactor was vented to normal pressure, the contents were removed from the reactor and cooled, and the supernatant paraffin wax was removed from the PFA aqueous dispersion. The solids concentration of the resulting PFA aqueous dispersion was 21.1% by mass. The resulting PFA aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, and coagulated under high-speed stirring conditions. The coagulated wet powder was dried at 150°C for 18 hours. The PFA powder had a melt flow rate of 64g / 10min, a melting point of 314.3°C, and a PPVE modification amount of 1.2 mol%.

[0545] Example 22 In a 6L stainless steel reactor equipped with a stirrer, 2980g of deionized water, 120g of paraffin wax, 4.5g of polymer A, and aqueous ammonia were added to adjust the pH to 9.1. The reactor contents were then heated to 70°C while being aspirated and purged with TFE to remove oxygen from the reactor. The contents were then stirred at 280 rpm. 0.27g of ethane gas and 26.4g of PPVE were added to the reactor, and TFE monomer was added until the pressure reached 0.73 MPaG. 150mg of ammonium persulfate (APS) initiator dissolved in 20g of deionized water was injected into the reactor, and the reactor was brought to a pressure of 0.83 MPaG. After the initiator was injected, a pressure drop occurred and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 0.78 MPaG. After the reaction started, 4.5g of PPVE was added for every 115g of TFE consumed. When the amount of TFE consumed in the reaction reached about 820 g, the supply of TFE and stirring were stopped. After that, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PFA aqueous dispersion. The solid content of the obtained PFA aqueous dispersion was 21.5% by mass. The obtained PFA aqueous dispersion was diluted with deionized water to a solid content of about 10% by mass, and coagulated under high-speed stirring conditions. The coagulated wet powder was dried at 150°C for 18 hours. The PFA powder had a melt flow rate of 12g / 10min, a melting point of 312.4°C, and a PPVE modification amount of 1.3 mol%.

[0546] Example 23 In a 1 L glass reactor equipped with a stirrer, 530 g of deionized water, 30 g of paraffin wax, 8.25 g of polymer A, and 55.0 mg of CH2=CF(CF2OCFCF3COONH4) were placed. Ammonia water was added to adjust the pH to 9.1. The reactor contents were then heated to 80°C while being aspirated and simultaneously purged with TFE monomer to remove oxygen from the reactor. The contents were then stirred at 540 rpm. 0.02 g of ethane gas and 16.8 g of HFP were added to the reactor, followed by TFE monomer to a pressure of 0.73 MPaG. 303 mg of ammonium persulfate (APS) initiator dissolved in 20 g of deionized water was injected into the reactor to bring the reactor to a pressure of 0.83 MPaG. After the initiator was injected, a pressure drop occurred and the initiation of polymerization was observed. TFE monomer was added to the reactor to keep the pressure constant at 0.78 MPaG. After the polymerization started, 27.5 mg of APS initiator dissolved in 5 g of deionized water was added every 5 hours. The polymerization was continued until about 120 g of TFE monomer had reacted. After that, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the FEP aqueous dispersion. The solids concentration of the resulting FEP aqueous dispersion was 18.3% by mass. A part of the obtained FEP aqueous dispersion was frozen in a freezer. The frozen FEP aqueous dispersion was left to stand until it reached 25°C, and a solidified powder was obtained. The solidified wet powder was dried at 150°C for 18 hours. The melt flow rate of the FEP powder at this time was 136g / 10min, the melting point was 282.3°C, and the HFP modification amount was 7.2 mol%.

[0547] Example 24 In a 6L SUS reactor equipped with a stirrer, 3560g of deionized water, 104g of paraffin wax, 53.4g of polymer A, 358.0mg of CH2=CF(CF2OCFCF3COONH4) and aqueous ammonia were added and the pH was adjusted to 9.1. The contents of the reactor were then heated to 80°C while being aspirated and purged with nitrogen gas at the same time to remove oxygen from the reactor. The contents were then stirred at 280 rpm. 100g of HFP was added to the reactor, and TFE monomer was added until the pressure reached 0.73MPaG. 1970mg of ammonium persulfate (APS) initiator dissolved in 20g of deionized water was injected into the reactor, and the reactor was brought to a pressure of 0.83MPaG. After the injection of the initiator, a drop in pressure occurred and the initiation of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 0.78MPaG. After the polymerization started, 180 mg of APS initiator dissolved in 10 g of deionized water was added every 5 hours. The polymerization was continued until about 900 g of TFE monomer had reacted. After that, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the PFA aqueous dispersion. The solids concentration of the resulting FEP aqueous dispersion was 20.3% by mass. A part of the obtained FEP aqueous dispersion was frozen in a freezer. The frozen FEP aqueous dispersion was left to stand until it reached 25°C, and a solidified powder was obtained. The solidified wet powder was dried at 150°C for 18 hours. The melt flow rate of the FEP powder at this time was 3.4g / 10min, the melting point was 249.7°C, and the HFP modification amount was 7.7mol%.

[0548] Example 25 1657g of deionized water and 3.0g of polymer A were added to a 3L SUS autoclave, the reactor was sealed, and the system was replaced with nitrogen to remove oxygen. The reactor was heated to 80°C, and while stirring, vinylidene fluoride [VDF] / tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] (=19 / 11 / 70 mol%) monomers (initial monomers) were pressed in to 1.53 MPaG. Then, a polymerization initiator solution in which 0.30g of ammonium persulfate (APS) was dissolved in deionized water was pressed in with nitrogen gas to start the reaction. As the polymerization progressed, when the internal pressure dropped to 1.50 MPaG, a mixed monomer of VDF / TFE / HFP (=50 / 20 / 30 mol%) was charged so that the internal pressure was constant at 1.53 MPaG. 0.15g of APS was dissolved in deionized water 100 minutes after the start of polymerization, 0.15g after 130 minutes, and 0.15g after 320 minutes, as described above, and the polymerization reaction was continued by injecting nitrogen gas. When 12g of the mixed monomer was added, 3.75g of diethyl malonate was injected as a chain transfer agent with nitrogen gas. When 261g of the mixed monomer was added, stirring was stopped and the reactor was depressurized until the pressure reached atmospheric pressure. The autoclave was cooled to obtain an aqueous dispersion with a solid content concentration of 13.1% by mass. The aqueous dispersion was added with an aqueous aluminum sulfate solution to carry out coagulation. The obtained coagulated product was washed with water and dried to obtain a rubber-like fluorocopolymer. The rubber-like fluorocopolymer had a Mooney viscosity of ML1+10 (100°C) = 21.1. The copolymer composition was examined by NMR analysis and found to be VDF / TFE / HFP = 50 / 20 / 30 (mol%).

[0549] Example 26 1657g of deionized water and 3.0g of polymer A were added to a 3L SUS autoclave, the reactor was sealed, and the system was replaced with nitrogen to remove oxygen. The reactor was heated to 80°C, and while stirring, vinylidene fluoride [VDF] / tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] (=19 / 11 / 70 mol%) monomers (initial monomers) were pressed in to 1.53 MPaG. Then, a polymerization initiator solution in which 0.030g of ammonium persulfate (APS) was dissolved in deionized water was pressed in with nitrogen gas to start the reaction. As the polymerization progressed, when the internal pressure dropped to 1.50 MPaG, a mixed monomer of VDF / TFE / HFP (=50 / 20 / 30 mol%) was charged so that the internal pressure was constant at 1.53 MPaG. 0.06g of APS was dissolved in deionized water 130 minutes after the start of polymerization, 0.30g after 300 minutes, and 0.30g after 370 minutes, as described above, and the polymerization reaction was continued by injecting nitrogen gas. When 12g of the mixed monomer was added, 2.907g of the diiodine compound I(CF2)4I was injected as a chain transfer agent with nitrogen gas. When 500g of the mixed monomer was added, stirring was stopped and the reactor was depressurized until the pressure reached atmospheric pressure. The autoclave was cooled to obtain an aqueous dispersion with a solid content concentration of 23.4% by mass. The aqueous dispersion was added with an aqueous aluminum sulfate solution to carry out coagulation. The obtained coagulated product was washed with water and dried to obtain a rubber-like fluorocopolymer. The rubber-like fluorocopolymer had a Mooney viscosity of ML1+10 (100°C) = 31.8. The copolymer composition was examined by NMR analysis and found to be VDF / TFE / HFP = 50 / 20 / 30 (mol%).

Claims

1. A method for producing a fluoropolymer, comprising the step of obtaining a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing polymerization units (1) based on a monomer represented by the following general formula (1), wherein the number average molecular weight of the polymer (1) is 0.3 × 10 4 or more: The fluoropolymer is a modified polytetrafluoroethylene, a melt-processable fluororesin, or a fluororubber, The modified polytetrafluoroethylene is a copolymer of tetrafluoroethylene and a modified monomer, The modified monomer is at least one selected from the group consisting of hexafluoropropylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group. CX ２ =CY(-CZ ２ -O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond; A is -COOM, -SO ３ M or -OSO ３ M (M is -H, a metal atom, -NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium; R ７ is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom.

2. The method according to claim 1, wherein at least one of X in the general formula (1) is -H.

3. The method according to claim 1 or 2, wherein in the general formula (1), both X's are -H.

4. The process according to any one of claims 1 to 3, wherein in general formula (1), Rf is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having 2 to 12 carbon atoms and an ether bond.

5. The method according to any one of claims 1 to 4, wherein the polymerized units (1) are polymerized units (1A) based on a monomer represented by the following general formula (1A): CH ２ =CF(-CF ２ -O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)

6. 2. The method according to claim 1, wherein the polymerized units (1) are polymerized units (1a) based on a fluoroallyl ether compound represented by the following general formula (1a): CX ２ =CFCF ２ -O-(CF(CF ３ )CF ２ O) ｎ５ -CF(CF ３ )-A (1a) (In the formula, each X is the same and represents F or H; n5 represents 0 or an integer of 1 to 10; and A is as defined above.)

7. The method according to any one of claims 1 to 6, wherein A is -COOM.

8. M is -H, -Na, -K, -Li or -NH ４ The method according to any one of claims 1 to 7, wherein

9. The method according to any one of claims 1 to 8, wherein the content of the polymerized units (1) in the polymer (1) is 90 mol % or more based on the total polymerized units.

10. The number average molecular weight of the polymer (1) is 1.0×10 ４ The method for producing according to any one of claims 1 to 9.

11. The number average molecular weight of the polymer (1) is 3.0×10 ４ The method for producing a semiconductor device according to any one of claims 1 to 10,

12. The method according to any one of claims 1 to 11, wherein the fluoropolymer is a modified polytetrafluoroethylene.

13. A method for producing an extruded body, comprising the step of extruding the modified polytetrafluoroethylene obtained by the method according to claim 12.

14. A composition comprising a fluoropolymer and a polymer (1) containing polymerization units (1) based on a monomer represented by the following general formula (1), wherein the number average molecular weight of the polymer (1) is 0.3 × 10 4 or more: The fluoropolymer is a modified polytetrafluoroethylene, a melt-processable fluororesin, or a fluororubber, The modified polytetrafluoroethylene is a copolymer of tetrafluoroethylene and a modified monomer, The composition, wherein the modified monomer is at least one selected from the group consisting of hexafluoropropylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group. CX ２ =CY(-CZ ２ -O-Rf-A) (1) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z may be the same or different and is -H, -F, an alkyl group or a fluoroalkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond; A is -COOM, -SO ３ M or -OSO ３ M (M is -H, a metal atom, -NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium; R ７ is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom.

15. The composition according to claim 14, wherein the polymerized units (1) are polymerized units (1A) based on a monomer represented by the following general formula (1A): CH ２ =CF(-CF ２ -O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)

16. The composition according to claim 14 or 15, wherein the content of the polymer (1) is from 0.0001% by mass to 20% by mass based on the fluoropolymer.

17. The composition according to any one of claims 14 to 16, wherein the fluoropolymer is a modified polytetrafluoroethylene.

18. 20. The composition of claim 17 which is extensible.

19. The composition according to claim 17, having a breaking strength of 10.0 N or more.

20. The composition according to claim 14, wherein the amount of the fluorine-containing surfactant is 10 ppm or less relative to the fluoropolymer.

21. The composition according to any one of claims 14 to 20, which is a powder.

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