Method for producing fluorine-containing polymer

Abstract

Provided is a novel method for producing a fluorine-containing polymer. A method for producing a fluorine-containing polymer, characterized by comprising a polymerization step for polymerizing tetrafluoroethylene in an aqueous medium in the presence of an initiator, a chain transfer agent, and a surfactant to obtain a fluorine-containing polymer containing more than 80 mol% of tetrafluoroethylene-based polymerization units, wherein the total amount of the chain transfer agent is added at one time, and the chain transfer agent is at least one selected from the group consisting of a disulfide ester compound, a dithiocarbamate compound, a trithiocarbonate compound, and a xanthate compound.

Description

[0001] This application is a divisional application of the original application with the Chinese national application number 202080089269.5, the filing date of December 17, 2020, and the invention title of “Method for producing fluorine-containing polymer”. TECHNICAL FIELD

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

[0003] As a method for producing fluorine-containing polymer, emulsion polymerization, solution polymerization is adopted.

[0004] For example, Patent Literature 1 describes a scheme in which tetrafluoroethylene, vinylidene fluoride, and hexafluoropropylene are polymerized in the presence of a microemulsion obtained in advance by mixing a perfluoropolyoxyalkylene having an acidic terminal group of the formula: CF2ClO(CF2-CF(CF3)O) n (CF2O) m CF2COOH (in the formula, n / m = 10, having an average molecular weight of 600) and a perfluoropolyether having an acidic terminal group of the formula: CF3O(CF2CF(CF3)O) n (CF2O) m CF3 and O-ethyl S-(1-methoxycarbonyl ethyl) dithiocarbonate as a chain transfer agent.

[0005] In addition, Patent Literature 2 describes a method for producing a polymer, characterized by bringing at least one of an ethylenically unsaturated monomer, at least one of a free radical source, and a compound of a specific structure into contact. Patent Literature 3 describes a method for producing a polymer, including: preparation of a microemulsion containing at least one control agent selected from xanthate, dithiocarbamate, thioether thione, and phosphorus-containing xanthate; and reaction of the above microemulsion in the presence of a free radical source.

[0006] Prior Art Documents

[0007] Patent Literature

[0008] Patent Literature 1: Japanese Patent Application Laid-Open No. 2017-515948

[0009] Patent Literature 2: Japanese Patent Application Laid-Open No. 2003-501528

[0010] Patent Literature 3: U.S. Patent No. 7317050 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] The present invention provides a novel production method of a fluoropolymer.

[0013] Means for solving the problem

[0014] The present invention relates to a production method of a fluoropolymer, characterized by comprising a polymerization step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of an initiator, a chain transfer agent, and a surfactant, to obtain a fluoropolymer containing a polymer unit based on tetrafluoroethylene of more than 80 mol% (hereinafter sometimes also referred to as "the first production method of the invention". In addition, in the present specification, when simply referred to as "the production method of the invention", it means "the first production method of the invention").

[0015] The fluoropolymer preferably contains a polymer unit based on tetrafluoroethylene of more than 90 mol%.

[0016] The fluoropolymer preferably contains only a polymer unit based on tetrafluoroethylene.

[0017] The fluoropolymer can further contain a polymer unit based on a monomer other than tetrafluoroethylene.

[0018] The monomer other than tetrafluoroethylene is preferably at least one selected from the group consisting of a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2).

[0019] General formula (1):

[0020] CF2=CR p R q

[0021] (In the formula, R p is H or F; R q is -Cl, -CF3, -R a , -COOR b , -OCOR c , -CONR d 2, -CN, -COR e , -Rf a , -ORf b ; R a , R b , R c , R d , and R e are the same or different and are H or a substituent; Rf a is a fluorine-containing alkyl group or a fluorine-containing vinyl group which can have a substituent and can contain an oxygen atom between carbon atoms; and Rf b is a fluorine-containing alkyl group; and Rp and R q may be bonded to each other to form a ring

[0022] General Formula (2):

[0023] CH2=CR s R t

[0024] (in the formula, R s is R g , -CF3or F; R t is -Cl, -R h , -COOR i , -OCOR j , -CONR k 2, -CN, -COR m , Rf c ; R g and R h are the same or different and are H or a hydrocarbon group or a heterocyclic group with or without a substituent; R i , R j , R k and R m are the same or different and are H or a substituent; Rf c is a fluorine-containing alkyl group, a fluorine-containing vinyl group or a fluorine-containing alkoxy group which can have a substituent and can contain an oxygen atom between carbon atoms; R s and R t may be bonded to each other to form a ring

[0025] The monomer other than tetrafluoroethylene described above is preferably at least one selected from the group consisting of hexafluoropropylene, trifluorochloroethylene, vinylidene fluoride, fluoroethylene, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl ester, (meth)acrylate, acrylamide, olefin, vinylamide, fluoroalkyl vinyl and fluorine-containing acrylate monomer.

[0026] The chain transfer agent described above is preferably a xanthate compound.

[0027] In the polymerization step described above, the concentration of the chain transfer agent with respect to the aqueous medium is preferably 0.1 x 10 -3 - 0.01 mol / liter.

[0028] The surfactant described above preferably does not contain a perfluoroalkyl group having 3 or more carbon atoms.

[0029] The present application also relates to a fluorine-containing polymer characterized by being represented by the formula: Af-CRP (in the formula, Af is a fluorine-containing polymer segment containing more than 80 mol% of polymerization units based on TFE. CRP is any one of the following formulas (CRP1) to (CRP5)).

[0030] Formula (CRP1):

[0031] -SC(S)Z c11

[0032] (in the formula, Z c11 is an alkyl group or an aryl group.)

[0033] Formula (CRP2):

[0034] -SC(S)SZ c12

[0035] (in the formula, Z c12 is an alkyl group or an aryl group.)

[0036] Formula (CRP3):

[0037] -SC(S)SR c11

[0038] (in the formula, R c11 is a monovalent organic group.)

[0039] Formula (CRP4):

[0040] -SC(S)NZ c13 2

[0041] (in the formula, Z c13 (i) is independently an alkyl group, an aryl group or a 4-pyridyl group, or (ii) is a group that is bonded to each other and forms a heterocycle together with the N atom in the formula.)

[0042] Formula (CRP5):

[0043] -SC(S)OZ c14

[0044] (in the formula, Z c14 is an alkyl group or an aryl group.)

[0045] In the above formula, Af preferably contains more than 90 mol% of polymerization units based on tetrafluoroethylene.

[0046] The fluorine-containing polymer of the present application is preferably represented by the following formula: Bf-CRP (in the formula, Bf is a fluorine-containing polymer segment containing only polymerization units based on tetrafluoroethylene. CRP is the same as described above).

[0047] The fluorine-containing polymer of the present application preferably has a molecular weight of 3000 or more.

[0048] Effects of the Invention

[0049] According to the present application, a novel production method of fluorine-containing polymer can be provided. DETAILED DESCRIPTION

[0050] Before the present application is described in detail, some terms used in the specification are defined or explained.

[0051] In the present specification, the fluororesin is a partially crystalline fluorine-containing polymer, and is a fluoroplastic. The fluororesin has a melting point, and has thermoplasticity, and can be melt-processable or non-melt-processable.

[0052] In the present specification, melt-processability means that the polymer can be processed by melting using existing processing equipment such as an extruder and an injection molding machine. Therefore, the fluororesin having melt-processability has a melt flow rate of usually 0.01 to 500 g / 10 minutes, measured by the following measuring method.

[0053] In the present specification, the perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule. The perfluoromonomer can also be a monomer in which several fluorine atoms bonded to a carbon atom are substituted with chlorine atoms, in addition to carbon atoms and fluorine atoms; and can also be a monomer having a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a boron atom, or a silicon atom, in addition to carbon atoms. As the perfluoromonomer, a monomer in which all hydrogen atoms are substituted with fluorine atoms is preferred. The perfluoromonomer does not include a monomer that provides a crosslinking site.

[0054] The monomer that provides a crosslinking site is a monomer (vulcanization site monomer) having a crosslinkable group that provides a crosslinking site for forming a crosslink with a curing agent to the fluorine-containing polymer.

[0055] In the present specification, the content of each monomer constituting the fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescence X-ray analysis according to the type of the monomer.

[0056] In the present specification, the "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound.

[0057] Examples of the "organic group" include:

[0058] an alkyl group which can have one or more substituent groups,

[0059] an alkenyl group which can have one or more substituent groups,

[0060] an alkynyl group which can have one or more substituent groups,

[0061] ​​cycloalkenyl group which can have one or more substituent (s),

[0062] cycloalkenyl group which can have one or more substituent (s),

[0063] cycloalkadienyl group which can have one or more substituent (s),

[0064] aryl group which can have one or more substituent (s),

[0065] aralkyl group which can have one or more substituent (s),

[0066] non-aromatic heterocyclic group which can have one or more substituent (s),

[0067] heteroaryl group which can have one or more substituent (s),

[0068] cyano group,

[0069] formyl group,

[0070] RaO-,

[0071] RaCO-,

[0072] RaSO2-,

[0073] RaCOO-,

[0074] RaNRaCO-,

[0075] RaCONRa-,

[0076] RaOCO-,

[0077] RaOSO2-, and

[0078] RaNRbSO2-

[0079] (these formulae, Ra is independently

[0080] alkyl group which can have one or more substituent (s),

[0081] alkenyl group which can have one or more substituent (s),

[0082] alkynyl group which can have one or more substituent (s),

[0083] cycloalkenyl group which can have one or more substituent (s),

[0084] cycloalkenyl group which can have one or more substituent (s),

[0085] cycloalkadienyl group which can have one or more substituent (s),

[0086] aryl group which can have one or more substituent (s),

[0087] an aralkyl group which can have 1 or more substituent (s),

[0088] a non-aromatic heterocyclic group which can have 1 or more substituent (s), or

[0089] a heteroaromatic group which can have 1 or more substituent (s),

[0090] Rb is independently H or an alkyl group which can have 1 or more substituent (s).

[0091] As the above-mentioned organic group, an alkyl group which can have 1 or more substituent (s) is preferable.

[0092] In addition, in the present specification, "substituent" means a substitutable group. Examples of the "substituent" include aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, acyloxy groups, acylamino groups, aliphatic oxy groups, aromatic oxy groups, heterocyclic oxy groups, aliphatic oxy carbonyl groups, aromatic oxy carbonyl groups, heterocyclic oxy carbonyl groups, carbamoyl groups, aliphatic sulfonyl groups, aromatic sulfonyl groups, heterocyclic sulfonyl groups, aliphatic sulfonyloxy groups, aromatic sulfonyloxy groups, heterocyclic sulfonyloxy groups, sulfamoyl groups, aliphatic sulfonylamino groups, aromatic sulfonylamino groups, heterocyclic sulfonylamino groups, amino groups, aliphatic amino groups, aromatic amino groups, heterocyclic amino groups, aliphatic oxy carbonylamino groups, aromatic oxy carbonylamino groups, heterocyclic oxy carbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxyl groups, cyano groups, sulfo groups, carboxyl groups, aliphatic oxy amino groups, aromatic oxy amino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxy oxyphosphino groups, and diarylatic oxy oxyphosphino groups.

[0093] The above-mentioned aliphatic group can be saturated or unsaturated, and can have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxy carbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, or the like. As the above-mentioned aliphatic group, an alkyl group having a total of 1 to 8, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, or the like, can be mentioned, and a part or all of the hydrogen atoms bonded to the carbon atom can be substituted with fluorine.

[0094] The above-mentioned aromatic group can have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxy carbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, or the like. As the above-mentioned aromatic group, an aryl group having 6 to 12, preferably a total of 6 to 10 carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylamino phenyl group, a 4-methane sulfonyl phenyl group, or the like, can be mentioned.

[0095] The above-mentioned heterocyclic group can have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxy carbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, and the like. As the above-mentioned heterocyclic group, a 5- to 6-membered heterocyclic group having a total of 2 to 12, preferably 2 to 10, carbon atoms can be mentioned, for example, a 2-tetrahydrofuranyl group, a 2-pyrimidinyl group, and the like.

[0096] The above-mentioned acyl group can have an aliphatic carbonyl group, an aryl carbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxy carbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, and the like. As the above-mentioned acyl group, an acyl group having a total of 2 to 8, preferably 2 to 4, carbon atoms can be mentioned, for example, an acetyl group, a propionyl group, a benzoyl group, a 3-pyridine carbonyl group, and the like.

[0097] The above-mentioned amido group can have an aliphatic group, an aromatic group, a heterocyclic group, and the like, for example, an acetylamino group, a benzoylamino group, a 2-pyridine carbonylamino group, a propionylamino group, and the like. As the above-mentioned amido group, an amido group having a total of 2 to 12, preferably 2 to 8, carbon atoms, an alkyl carbonyl amino group having a total of 2 to 8 carbon atoms, for example, an acetylamino group, a benzoylamino group, a 2-pyridine carbonylamino group, a propionylamino group, and the like can be mentioned.

[0098] The above-mentioned aliphatic oxy carbonyl group can be saturated or unsaturated, and can have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxy carbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, and the like. As the above-mentioned aliphatic oxy carbonyl group, an alkoxy carbonyl group having a total of 2 to 8, preferably 2 to 4, carbon atoms can be mentioned, for example, a methoxy carbonyl group, an ethoxy carbonyl group, a (tert) butoxy carbonyl group, and the like.

[0099] The above-mentioned carbamoyl group can have an aliphatic group, an aromatic group, a heterocyclic group, and the like. As the above-mentioned carbamoyl group, an unsubstituted carbamoyl group, an alkyl carbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, an alkyl carbamoyl group having a total of 2 to 5 carbon atoms can be mentioned, for example, an N-methyl carbamoyl group, an N,N-dimethyl carbamoyl group, an N-phenyl carbamoyl group, and the like.

[0100] The above-mentioned aliphatic sulfonyl group can be saturated or unsaturated, and can have a hydroxyl group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxy carbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, and the like. As the above-mentioned aliphatic sulfonyl group, an alkyl sulfonyl group having a total of 1 to 6, preferably 1 to 4, carbon atoms can be mentioned, for example, a methane sulfonyl group, and the like.

[0101] The above-mentioned aromatic sulfonyl group can 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 amido group, a carbamoylamino group, and the like. As the above-mentioned aromatic sulfonyl group, an arylsulfonyl group having a total of 6 to 10 carbon atoms, such as a benzenesulfonyl group, and the like can be given.

[0102] The above-mentioned amino group can have an aliphatic group, an aromatic group, a heterocyclic group, and the like.

[0103] The above-mentioned amido group can have, for example, an acetylamino group, a benzoylamino group, a 2-pyridylcarbonylamino group, a propionylamino group, and the like. As the above-mentioned amido group, an amido group having a total of 2 to 12 carbon atoms, preferably an amido group having a total of 2 to 8 carbon atoms, more preferably an alkylcarbonylamino group having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridylcarbonylamino group, a propionylamino group, and the like can be given.

[0104] The above-mentioned aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group can be, for example, a methylsulfonamide group, a phenylsulfonamide group, a 2-pyridylsulfonamide group, and the like.

[0105] The above-mentioned sulfamoyl group can have an aliphatic group, an aromatic group, a heterocyclic group, and the like. As the above-mentioned sulfamoyl group, 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, a heterocyclicsulfamoyl 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, a heterocyclicsulfamoyl group having a total of 2 to 10 carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, a N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, a 4-pyridylsulfamoyl group, and the like can be given.

[0106] The above-mentioned aliphatic oxy group can be saturated or unsaturated, and can have a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a methoxyethyloxy group, and the like. As the above-mentioned aliphatic oxy group, 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 isopropoxy group, a cyclohexyloxy group, a methoxyethyloxy group, and the like can be given.

[0107] The above-mentioned aromatic amino group, heterocyclic amino group can have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused to the aryl group, an aliphatic oxycarbonyl group, an aliphatic group having a total of 1 to 4 carbon atoms, an aliphatic oxy group having a total of 1 to 4 carbon atoms, a halogen atom, a carbamoyl group having a total of 1 to 4 carbon atoms, a nitro group, an aliphatic oxycarbonyl group having a total of 2 to 4 carbon atoms, and the like.

[0108] The above-mentioned aliphatic sulfonyl group can be saturated or unsaturated, and examples of the aliphatic sulfonyl group include alkylsulfonyl groups having a total of 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, carbamoylmethylsulfonyl, tert-butylsulfonyl, and the like.

[0109] The above-mentioned carbamoylamino group can have an aliphatic group, an aryl group, a heterocyclic group, or the like. As the carbamoylamino group, examples include carbamoylamino, alkylcarbamoylamino groups having a total of 2 to 9 carbon atoms, dialkylcarbamoylamino groups having a total of 3 to 10 carbon atoms, arylcarbamoylamino groups having a total of 7 to 13 carbon atoms, heterocycliccarbamoylamino groups having a total of 3 to 12 carbon atoms, preferably carbamoylamino, alkylcarbamoylamino groups having a total of 2 to 7 carbon atoms, dialkylcarbamoylamino groups having a total of 3 to 6 carbon atoms, arylcarbamoylamino groups having a total of 7 to 11 carbon atoms, heterocycliccarbamoylamino groups having a total of 3 to 10 carbon atoms, such as carbamoylamino, methylcarbamoylamino, N,N-dimethylcarbamoylamino, phenylcarbamoylamino, 4-pyridylcarbamoylamino, and the like.

[0110] In addition, in the present specification, a range indicated by an end point includes all numerical values included in the range (for example, 1.4, 1.9, 2.33, 5.75, 9.98, and the like are included in 1 to 10).

[0111] In addition, in the present specification, "at least 1" includes all numerical values of 1 or more (for example, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, and the like).

[0112] The present application will be described in detail below.

[0113] The production method of the present application is characterized by including a polymerization step of polymerizing tetrafluoroethylene [TFE] in an aqueous medium in the presence of an initiator, a chain transfer agent, and a surfactant, the fluoropolymer containing a TFE-based polymer unit of greater than 80 mol%.

[0114] In the production method of the present application, by polymerizing TFE in the presence of an initiator, a specific chain transfer agent, and a surfactant, polymerization can be performed even when the proportion of TFE is large, that is, when the TFE-based polymer unit is greater than 80 mol%. The above-mentioned polymerization is so-called emulsion polymerization.

[0115] The production method of the present application is characterized by including a polymerization step of polymerizing tetrafluoroethylene [TFE] in an aqueous medium in the presence of an initiator, a chain transfer agent, and a surfactant, the fluoropolymer containing a TFE-based polymer unit of greater than 80 mol%.

[0116] In the case of polymerizing a fluoropolymer having a large number of polymer units based on TFE, a chain transfer agent is not generally used for the reason that the molecular weight is decreased. In the production method of the present application, even in the case of polymerizing a fluoropolymer having a large number of polymer units based on TFE, it was surprisingly found that polymerization can be efficiently carried out, thereby completing the present application.

[0117] The above chain transfer agent is at least one selected from the group consisting of a dithioester compound, a dithio carbamate compound, a trithiocarbonate compound and a xanthate compound. As the above chain transfer agent, at least one selected from the group consisting of a dithio carbamate compound and a xanthate compound is preferred, and a xanthate compound is more preferred.

[0118] As the above chain transfer agent, specifically, a dithioester represented by Formula (cl-1), a trithiocarbonate represented by Formula (cl-2) or Formula (cl-2'), a dithio carbamate represented by Formula (cl-3), a xanthate represented by Formula (cl-4) can be mentioned.

[0119] [Chemical Formula 1]

[0120]

[0121] In Formulas (cl-1) to (cl-4), Z c1 is an aryl group or an alkyl group, for example, a phenyl group, a cyano phenyl group, or the like aryl group having 6 to 20 carbon atoms, an ethyl group, or the like alkyl group having 1 to 15 carbon atoms. Z c2 is an aryl group or an alkyl group, for example, a dodecyl group, or the like alkyl group having 1 to 15 carbon atoms. Z c3 and Z c4 each independently is an alkyl group, an aryl group or a 4-pyridyl group, for example, a methyl group, or the like alkyl group having 1 to 15 carbon atoms, a phenyl group, or the like aryl group having 6 to 20 carbon atoms. Z c3 and Z c4 may be bonded to each other and form a heterocyclic ring such as a pyrrole ring, a pyrrolidone ring, or the like together with the N atom in Formula (cl-3). Z c5 is an aryl group or an alkyl group, for example, an ethyl group, a trifluoroethyl group, or the like alkyl group having 1 to 15 carbon atoms, a phenyl group, a perfluoro phenyl group, or the like aryl group having 6 to 20 carbon atoms.

[0122] Z c5 Among them, the aryl group is preferably a phenyl group, a cyano phenyl group or a perfluoro phenyl group, and more preferably a phenyl group or a perfluoro phenyl group.

[0123] The above Z c5 Among them, the alkyl group is preferably a methyl group, an ethyl group, a butyl group, a dodecyl group or a trifluoroethyl group, and more preferably a methyl group, an ethyl group or a trifluoroethyl group.

[0124] In formulae (c1-1) to (c1-4), R r is a monovalent organic group, and examples thereof include (i) an alkyl group, and (ii) a group in which one or more than two of the hydrogen atoms of the alkyl group are substituted with at least one selected from the group consisting of a phenyl group, a cyano group, a hydroxyl group, a carboxyl group, a carboxyalkyl group having 1 to 4 carbon atoms, a phenoxyalkyl group having 1 to 4 carbon atoms, an acetoxy group, and a group represented by c1 to c4 below.

[0125] In formula (c1-2'), two R r may be the same or different.

[0126] R r The alkyl group has usually 1 to 18, preferably 2 to 12 carbon atoms.

[0127] [Chemical Formula 2]

[0128]

[0129] In formulae (c1) to (c4) above, * indicates a bonding site. In formula c2 above, A c is an alkylene group having 2 to 5 carbon atoms, and n is an integer of 10 to 300.

[0130] As the dithioester (c1-1), for example, the following compound can be given.

[0131] [Chemical Formula 3]

[0132]

[0133] As the trithiocarbonates (c1-2) and (c1-2'), for example, the following compounds can be given.

[0134] [Chemical Formula 4]

[0135]

[0136] [Chemical Formula 5]

[0137]

[0138] (In the formula, n is an integer of 10 to 300.)

[0139] As the dithioamino acid ester (c1-3), for example, the following compound can be given.

[0140] [Chemical Formula 6]

[0141]

[0142] As the xanthic acid ester (c1-4), for example, the following compound can be given.

[0143] [Chemical Formula 7]

[0144]

[0145] (In the formula, n is an integer of 1 to 50.)

[0146] Among them, the following compound (O-ethyl S-(1-methoxycarbonyl ethyl) dithiocarbonate) is preferred.

[0147] [Chemical 8]

[0148]

[0149] In the above polymerization step, the concentration of the above chain transfer agent with respect to the aqueous medium is preferably 0.1 x 10 -3 to 0.01 mol / L. By making the concentration of the above chain transfer agent within the above range, the polymerization can be performed more efficiently. The concentration of the above chain transfer agent with respect to the aqueous medium is more preferably 0.2 x 10 -3 mol / L or more, further preferably 0.3 x 10 -3 mol / L or more, and even more preferably 0.9 x 10 -2 mol / L or less, further preferably 0.8 x 10 -2 mol / L or less.

[0150] By using the above chain transfer agent, reversible addition fragmentation chain transfer polymerization (RAFT) can be performed. In RAFT, living radical polymerization can be performed in the presence of the above chain transfer agent.

[0151] In the production method of the present application, TFE is polymerized in the presence of an initiator. As a suitable initiator, peroxide, inorganic agent, and initiators of azo compounds and redox systems can be given.

[0152] As specific examples of the peroxide initiator, hydrogen peroxide, sodium peroxide or barium peroxide, diacetyl peroxide, disuccinyl peroxide, dipropionyl peroxide, dibutyryl peroxide, dibenzoyl peroxide, benzoyl acetyl peroxide, diglutaroyl peroxide, and diallaeyl peroxide, and the like diacyl peroxides, and peracids and salts thereof (for example, ammonium salt, sodium salt, potassium salt) can be given. As an example of the peracid, peracetic acid can be given. Esters of peracids can also be used, and as examples thereof, t-butyl peroxy acetate and t-butyl peroxy pivalate can be given.

[0153] As examples of the above inorganic agent, for example, ammonium, alkali metal or alkaline earth salts of peroxidesulfuric acid, permanganic acid or manganic acid, or manganic acid can be given. A persulfate initiator such as ammonium persulfate (APS) can be used alone, or can also be used in combination with a reducing agent. As a suitable reducing agent, for example, hydrosulfite salts such as ammonium bisulfite or sodium metabisulfite; thiosulfate salts such as ammonium thiosulfate, potassium thiosulfate or sodium thiosulfate; hydrazine, azodicarboxylic esters and azodicarboxylic diamide (ADA) can be given. As a further usable reducing agent, for example, sodium formaldehyde sulfoxylate (Rongalit) or fluoroalkylsulfinate salts disclosed in the specification of U.S. Patent No. 5,285,002 can be given. The reducing agent typically reduces the half-life of the persulfate initiator. Further, a metal salt catalyst such as a copper salt, an iron salt or a silver salt can be added.

[0154] As the azo compound, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-imidazolinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylhydrazine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(isobutylamide) dihydrate, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-cyanopropanol), dimethyl-2,2'-azobis(2-methylpropionamide), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] can be given.

[0155] As the above initiator, a peracid ester, a persulfate, a diacyl peroxide, 2,2'-azobis(2-methylbutyronitrile) or 2,2'-azobis(2-methylbutyronitrile) is more preferable, and tert-butyl peroxypivalate, dibenzoyl peroxide, tert-butyl peroxyacetate or 2,2'-azobis(2-methylbutyronitrile) is further preferable.

[0156] In the above polymerization step, the concentration of the above initiator with respect to the aqueous medium is preferably 1 x 10 -5 -0.01 mole / liter. By making the concentration of the above initiator within the above range, polymerization can be performed more efficiently. The concentration of the above initiator with respect to the aqueous medium is more preferably 2 x 10 -5 mole / liter or further preferably 3 x 10 -5 mole / liter or further preferably 3 x 10 -20.8 x 10 -2 0.8 x 10

[0157] From the viewpoint of efficiently performing polymerization, the above-mentioned molar ratio of the chain transfer agent to the initiator [chain transfer agent] / [initiator] is preferably 0.1 to 40. More preferably, it is 0.2 to 30, further preferably 0.3 to 20, further more preferably 0.4 to 15, and particularly preferably 0.5 to 10.

[0158] By setting the molar ratio of the initiator to the chain transfer agent to a specific range as described above, polymerization can be efficiently performed.

[0159] The above-mentioned surfactant is not particularly limited, and a fluorine-containing surfactant, a hydrocarbon-based surfactant, or the like can be given.

[0160] The above-mentioned fluorine-containing surfactant can be a fluorine-containing anionic surfactant, or the like.

[0161] The above-mentioned fluorine-containing anionic surfactant can be, for example, a surfactant containing a fluorine atom having a total number of carbon atoms other than the anion group Y 0 in the following general formula (N 0 ) of 20 or less.

[0162] The above-mentioned fluorine-containing surfactant can also be a fluorine-containing surfactant having a molecular weight of the anion portion of 800 or less.

[0163] Note that the above-mentioned "anion portion" refers to a portion other than the cation of the above-mentioned fluorine-containing surfactant. For example, in the case of F(CF2) n1 COOM represented by the following formula (I), it is the portion of "F(CF2) n1 COO".

[0164] In addition, as the above-mentioned fluorine-containing surfactant, a fluorine-containing surfactant having a LogPOW of 3.5 or less, preferably 3.4 or less can be given. The above-mentioned LogPOW is the partition coefficient of 1-octanol to water, and is represented by LogP [in the formula, P represents the ratio of the concentration of the fluorine-containing surfactant in octanol to the concentration of the fluorine-containing surfactant in water when phase separation occurs in an octanol / water (1:1) mixed solution containing the fluorine-containing surfactant].

[0165] The above LogPOW is calculated as follows: HPLC is performed on standard substances (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) having a known octanol / water partition coefficient under the following conditions: column: TOSOH ODS-120T column (φ 4.6 mm x 250 mm, manufactured by TOSOH CORPORATION), eluent: acetonitrile / 0.6 mass% HCIO4 water = 1 / 1 (vol / vol%), flow rate: 1.0 ml / min, sample amount: 300 μL, column temperature: 40°C, detection light: UV 210 nm, a calibration curve of each elution time and the known octanol / water partition coefficient is prepared, and the LogPOW is calculated from the elution time in the HPLC of the sample liquid based on the calibration curve.

[0166] As the above-mentioned fluorine-containing surfactant, specifically, there can be mentioned fluorine-containing surfactants described in U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 142541, U.S. Patent Application Publication No. 2008 / 0015319, U.S. Patent No. 3250808, U.S. Patent No. 3271341, Japanese Patent Application Laid-Open No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, International Publication No. 2007 / 119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, International Publication No. 2013 / 189826, and the like.

[0167] As the above-mentioned fluorine-containing anionic surfactant, there can be mentioned fluorine-containing anionic surfactants of the following general formula (N 0 ):

[0168] X n0 -Rf n0 -Y 0 (N 0 )

[0169] (In the formula, X n0 is H, Cl, or / and F. Rf n0 is a chain, branched, or cyclic alkylene group having 3 to 20 carbon atoms, in which part or all of H is substituted with F, the alkylene group can contain one or more ether bonds, and part of H can be substituted with Cl. Y 0an anion group).

[0170] Y 0 The anion group of -COOM, -SO2M or -SO3M, or -COOM or -SO3M.

[0171] M is H, a metal atom, NR 7 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 7 is H or an organic group.

[0172] As the above metal atom, an alkali metal (Group 1), an alkaline earth metal (Group 2), etc., for example, Na, K or Li can be given.

[0173] As R 7 , H or a C 1-10 1-10 alkyl group can be given. 1-4 As the organic group of R 1-4 , an alkyl group can be given.

[0174] M can be H, a metal atom or NR 7 4, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4, H, Na, K, Li or NH4.

[0175] In the above Rf n0 , 50% or more of H can be substituted with fluorine.

[0176] As the compound represented by the above general formula (N 0 ), the following can be given:

[0177] the following general formula (N 1 ) :

[0178] X n0 -Rf m -Y 0 (N 1 )

[0179] (In the formula, X n0 is H, Cl and F, Rf m is a straight chain or branched chain perfluoroalkylene group having 3 to 15 carbon atoms, and Y 0 is the above definition), more specifically, the following general formula (N 1a ) :

[0180] X n0 -(CF2) m1 -Y 0 (N 1a )

[0181] (in the formula, Rf n0 is H, Cl and F, m1 is an integer of 3 to 15, Y 0 is the compound represented by the above formula);

[0182] the following general formula (N 2 ):

[0183] Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 )

[0184] (in the formula, Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, X n1 is F or CF3, Y 0 is the compound represented by the above formula);

[0185] the following general formula (N 3 ):

[0186] Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 )

[0187] (in the formula, Rf n2 is a partially or completely fluorinated alkyl group having 1 to 13 carbon atoms which can 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, Y 0 is the compound represented by the above formula);

[0188] the following general formula (N 4 ):

[0189] Rf m4 -O-L 4 -Y 0 (N 4 )

[0190] (in the formula, Rf m4 is a partially or completely fluorinated aliphatic group which can contain an ether bond, L 4 represents a partially or completely fluorinated linear alkylene group or aliphatic hydrocarbon group, Y 0 is the compound represented by the above formula (more specifically, the following general formula (N 4a):

[0191] Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4a )

[0192] (Where Rf n4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and which may contain an ether bond, n1 and Y n2 The same or different, H or F, p is 0 or 1, Y 0 (a compound represented by the above definition); and

[0193] The following general formula (N 5 ):

[0194] [Chemistry 9]

[0195]

[0196] (Where, X n2 、X n3 and X n4 Rf may be the same or different and is H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond. n5 is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms and may contain an ether bond, L is a connecting group, Y 0 As defined above. n2 、X n3 、X n4 and Rf n5 The compound represented by (the total number of carbon atoms is 18 or less).

[0197] As the above general formula (N 0), more specifically, there can be mentioned a perfluorocarboxylic acid (I) represented by the following general formula (I), an ω-H perfluorocarboxylic acid (II) represented by the following general formula (II), a perfluoropolyether carboxylic acid (III) represented by the following general formula (III), a perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), a perfluoroalkoxyfluorocarboxylic acid (V) represented by the following general formula (V), a perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), an ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), a perfluoroalkylalkylenesulfonic acid (VIII) represented by the following general formula (VIII), an alkylalkylene carboxylic acid (IX) represented by the following general formula (IX), a fluorocarboxylic acid (X) represented by the following general formula (X), an alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI) and a compound (XII) represented by the following general formula (XII).

[0198] The above-mentioned perfluorocarboxylic acid (I) is represented by the following general formula (I):

[0199] F(CF2) n1 COOM (I)

[0200] (where n1 is an integer from 3 to 14, M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group).

[0201] The above-mentioned ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II):

[0202] H(CF2) n2 COOM (II)

[0203] (wherein n2 is an integer from 4 to 15, and M is as defined above).

[0204] The above-mentioned perfluoropolyether carboxylic acid (III) is represented by the following general formula (III):

[0205] Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III)

[0206] (Where 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).

[0207] As the above perfluoropolyether carboxylic acid (III), a perfluoropolyether carboxylic acid having a total number of carbon atoms of 7 or less and a LogPOW of 3.5 or less is preferred. The above total number of carbon atoms is particularly preferably 5 to 7. Further, the above LogPOW is more preferably 3.4 or less.

[0208] The above perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV)

[0209] Rf 2 (CH2) n4 Rf 3 COOM (IV)

[0210] (in the formula, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above).

[0211] The above alkoxyfluorocarboxylic acid (V) is represented by the following general formula (V)

[0212] Rf 4 -O-CY 1 Y 2 CF2-COOM (V)

[0213] (in the formula, Rf 4 is a linear or branched partially or completely fluorinated alkyl group having 1 to 12 carbon atoms which can 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).

[0214] The above perfluoroalkyl sulfonic acid (VI) is represented by the following general formula (VI)

[0215] F(CF2) n5 SO3M (VI)

[0216] (in the formula, n5 is an integer of 3 to 14, and M is as defined above).

[0217] The above ω-H perfluoro sulfonic acid (VII) is represented by the following general formula (VII)

[0218] H(CF2) n6 SO3M (VII)

[0219] (in the formula, n6 is an integer of 4 to 14, and M is as defined above).

[0220] The above perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII)

[0221] Rf 5(CH2) n7 SO3M (VIII)

[0222] (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).

[0223] The above alkylalkylene carboxylic acid (IX) is represented by the following general formula (IX)

[0224] Rf 6 (CH2) n8 COOM (IX)

[0225] (in the formula, Rf 6 is a linear or branched partially or completely fluorinated alkyl group having 1 to 13 carbon atoms which can contain an ether bond, n8 is an integer of 1 to 3, and M is as defined above).

[0226] The above fluorocarboxylic acid (X) is represented by the following general formula (X)

[0227] Rf 7 -O-Rf 8 -O-CF2-COOM (X)

[0228] (in the formula, Rf 7 is a linear or branched partially or completely fluorinated alkyl group having 1 to 6 carbon atoms which can contain an ether bond, Rf 8 is a linear or branched partially or completely fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above).

[0229] The above alkoxyfluorosulfonic acid (XI) is represented by the following general formula (XI)

[0230] Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI)

[0231] (in the formula, Rf 9 is a linear or branched partially or completely fluorinated alkyl group having 1 to 12 carbon atoms which can contain an ether bond and can contain chlorine, Y 1 and Y 2 are the same or different and are H or F, and M is as defined above).

[0232] The above compound (XII) is represented by the following general formula (XII) :

[0233] [Chem. 10]

[0234]

[0235] (in the formula, X1 , X 2 and X 3 may be the same or different, and are H, F, and a linear or branched chain moiety which can contain an ether bond or a fully fluorinated alkyl group having 1 to 6 carbon atoms, Rf 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, Y 0 is an anionic group).

[0236] Y 0 may be -COOM, -SO2M, or -SO3M, and can be -SO3M or COOM (in the formula, M is as defined above).

[0237] As L, for example, a single bond, a moiety which can contain an ether bond or a fully fluorinated alkylene group having 1 to 10 carbon atoms can be mentioned.

[0238] As the above-mentioned fluorine-containing anionic surfactant, a carboxylic acid-based surfactant, a sulfonic acid-based surfactant, and the like can be mentioned.

[0239] Among the above-mentioned fluorine-containing anionic surfactants, in the case of using a compound represented by the general formula (N 1 ), Rf 1 in the formula (N m ) preferably has an integer of 3 to 6 carbon atoms. Further, m1 in the formula (N 1a ) preferably has an integer of 3 to 6. Further, in the case of using the perfluorocarboxylic acid (I), n1 in the general formula (I) preferably has an integer of 3 to 6.

[0240] As the above-mentioned fluorine-containing anionic surfactant, a compound selected from the group consisting of fluorine-containing carboxylic acids having 4 to 7 carbon atoms which can have an etheric oxygen, and salts thereof is particularly preferred. Here, the number of carbon atoms refers to the total number of carbon atoms in one molecule. Two or more kinds of the above-mentioned fluorine-containing anionic surfactants can be used in combination.

[0241] As the above-mentioned fluorine-containing anionic surfactant, a compound selected from the group consisting of fluorine-containing carboxylic acids having 4 to 7 carbon atoms which have an etheric oxygen, and salts thereof is preferred. The fluorine-containing carboxylic acid having an etheric oxygen is a compound having 4 to 7 carbon atoms, having an etheric oxygen in the middle of the main chain carbon chain, and having -COOH at the terminal. The terminal -COOH can form a salt.

[0242] The etheric oxygen present in the middle of the main chain is one or more, preferably 1 to 4, more preferably 1 or 2.

[0243] The above-mentioned number of carbon atoms is preferably 5 to 7.

[0244] As the above-mentioned fluorine-containing anion surfactant, it is particularly preferable that the number of carbon atoms in the main chain be 6 to 7, the number of etheric oxygen in the main chain be 1 to 4, and the main chain have a carboxylic acid or a salt thereof that is partially or completely fluorinated and has a linear, branched, or cyclic shape. Here, the "main chain" refers to the longest continuous chain.

[0245] As such a fluorine-containing surfactant, CF3O(CF2)3OCHFCF2COONH4, CF3CF2CF2OCF(CF3)COONH4, CF3CF2OCF2CF2OCF2COONH4, CF3OCF(CF3)CF2OCF(CF3)COONH4, the following formula:

[0246] [Chemical 11]

[0247]

[0248] the compound represented by.

[0249] As the above-mentioned hydrocarbon-based surfactant, for example, substances described in Japanese Patent Application Laid-Open No. 2013-542308, Japanese Patent Application Laid-Open No. 2013-542309, and Japanese Patent Application Laid-Open No. 2013-542310, or the like can be used.

[0250] The above-mentioned hydrocarbon-based surfactant can be a surfactant having a hydrophilic portion and a hydrophobic portion on the same molecule. They can be cationic, nonionic, or anionic.

[0251] Cationic hydrocarbon-based surfactants generally have a positively charged hydrophilic portion such as an alkylated ammonium halide (such as an alkylated ammonium bromide, etc.), and a hydrophobic portion such as a long-chain fatty acid.

[0252] Anionic hydrocarbon-based surfactants generally have a hydrophilic portion such as a carboxylate, sulfonate, or sulfate, and a hydrophobic portion such as an alkyl group as a long-chain hydrocarbon portion.

[0253] Nonionic hydrocarbon-based surfactants generally do not contain a charged group and have a hydrophobic portion that is a long-chain hydrocarbon. The hydrophilic portion of a nonionic surfactant contains a water-soluble functional group such as an ethylene glycol ether chain derived from polymerization with ethylene oxide.

[0254] Examples of nonionic hydrocarbon-based surfactants:

[0255] polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, derivatives thereof.

[0256] Specific examples of the polyoxyethylene alkyl ether: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like.

[0257] Specific examples of the polyoxyethylene alkyl phenyl ether: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, and the like.

[0258] Specific examples of the polyoxyethylene alkyl ester: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, and the like.

[0259] Specific examples of the sorbitan alkyl ester: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like.

[0260] Specific examples of the polyoxyethylene sorbitan alkyl ester: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and the like.

[0261] Specific examples of the glycerin ester: glyceryl monomyristate, glyceryl monostearate, glyceryl monooleate, and the like.

[0262] Specific examples of the above derivative: polyoxyethylene alkyl amine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, and the like.

[0263] The above ether and ester can have an HLB value of 10 to 18.

[0264] As the nonionic hydrocarbon-based surfactant, Triton (registered trademark) X series (X15, X45, X100, and the like) manufactured by Dow Chemical Company, Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, and the like), Tergitol (registered trademark) L series, Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)) manufactured by BASF, Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10), and the like can be given.

[0265] As the anionic hydrocarbon-based surfactant, Versatic (registered trademark) 10 of Resolution Performance Products, Avanel S series (S-70, S-74, and the like) manufactured by BASF, and the like can be given.

[0266] The above hydrocarbon-based surfactant can be a surfactant not containing a fluorine atom, preferably a surfactant having a linear or branched alkyl group having a carbon number of 8 to 30 which can have a substituent or a linking group (carbonyl, ether, ester, amide, sulfonyl, etc.) and a hydrophilic group (carbonyl, ether, ester, amide, sulfonyl, etc.) and not containing a fluorine atom, or a hydrocarbon-based anionic surfactant not containing a fluorine atom.

[0267] As the above hydrocarbon-based surfactant, a hydrocarbon-based surfactant of anionic type is preferred.

[0268] As the above hydrocarbon-based surfactant of anionic type, a surfactant represented by R z -L-M (in the formula, R z is a linear or branched alkyl group having a carbon number of 1 or more with or without a substituent or a cyclic alkyl group having a carbon number of 3 or more with or without a substituent, and in the case of a carbon number of 3 or more, can include a 1- or 2-valent heterocycle, and can be ringed. L is -ArSO3 - , -SO3 - , -SO4 - , -PO3 - , or -COO - , and M is H, a metal atom, NR 5z 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 5z is H or an organic group, and -ArSO3 - is an aryl sulfonate) can be mentioned.

[0269] Specifically, a substance represented by CH3-(CH2) n -L-M (in the formula, n is an integer of 6 to 17. L and M are the same as above) can be mentioned.

[0270] A mixture of a substance in which R z is an alkyl group having 12 to 16 carbon atoms, and L-M is a sulfate or sodium dodecyl sulfate (SDS) can also be used.

[0271] As the above hydrocarbon-based surfactant of anionic type, a surfactant represented by R 6z (-L-M)2(in the formula, R 6z is a linear or branched alkylene group having a carbon number of 1 or more with or without a substituent or a cyclic alkylene group having a carbon number of 3 or more with or without a substituent, and in the case of a carbon number of 3 or more, can include a 1- or 2-valent heterocycle, and can be ringed. L is -ArSO3 - , -SO3 - , -SO4- 、-PO3 - or -COO - , M is H, metal atom, NR 5z 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5z H or an organic group, -ArSO3 - Anionic surfactant represented by aryl sulfonate).

[0272] Examples of the anionic hydrocarbon surfactants include those composed of R 7z (-LM)3(where R 7z It is a linear or branched alkynyl group with or without a substituent having 1 or more carbon atoms, or a cyclic alkynyl group with or without a substituent having 3 or more carbon atoms. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or may be coiled in a ring. L is -ArSO3 - 、-SO3 - 、-SO4 - 、-PO3 - or -COO - , M is H, metal atom, NR 5z 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 5z Is H or an organic group. -ArSO3 - Anionic surfactant represented by aryl sulfonate).

[0273] The above R 5z It is preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms.

[0274] Examples of siloxane hydrocarbon surfactants include those described in Silicone Surfactants, RMHill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of siloxane surfactants consists of a distinct hydrophobic portion and a hydrophilic portion. The hydrophobic portion comprises one or more dihydrocarbylsiloxane units, where all the substituents on the silicon atoms are hydrocarbons.

[0275] When the carbon atoms of the hydrocarbon group may be substituted by halogens such as fluorine, complete substitution by hydrogen atoms means that these siloxane surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituent on the carbon atom of the hydrocarbon group is hydrogen.

[0276] The hydrophilic portion of the silicone hydrocarbon surfactant can include one or more polar moieties including sulfate, sulfonate, phosphonate, phosphate ester, carboxylate, carbonate, sulfosuccinate, taurinate (as a free acid, salt, or ester), phosphine oxide, betaine, betaine co-polyol, quaternary ammonium salt zwitterionic group. The ionic hydrophobic portion can also include an ionically functionalized silicone graft.

[0277] As such silicone hydrocarbon surfactants, for example, polydimethylsiloxane-grafted-(meth)acrylate, polydimethylsiloxane-grafted-polyacrylate, and polydimethylsiloxane grafted quaternary amine can be cited.

[0278] The polar moieties of the hydrophilic portion of the silicone surfactant can include polyethylene oxide (PEO) and mixed polyethylene oxide / propylene oxide polyether (PEO / PPO) and the like polyethers; monosaccharides and disaccharides; and water-soluble heterocycles such as pyrrolidone to form nonionic groups. The ratio of ethylene oxide to propylene oxide (EO / PO) can vary in the mixed polyethylene oxide / propylene oxide polyether.

[0279] The hydrophilic portion of the silicone hydrocarbon surfactant can also include a combination of ionic and nonionic moieties. As such moieties, for example, ionically end-functionalized or randomly functionalized polyethers or polyols can be cited. Preferred in the practice of the present application is a silicone having a nonionic moiety, i.e., a nonionic silicone surfactant.

[0280] In the structure of the silicone hydrocarbon surfactant, the arrangement of the hydrophobic and hydrophilic portions can take the form of a diblock polymer (AB), a triblock polymer (ABA) (here, "B" represents the silicone portion of the molecule), or a multiblock polymer. Alternatively, the silicone surfactant can include a graft polymer.

[0281] With respect to silicone hydrocarbon surfactants, there is also disclosure in U.S. Patent No. 6,841,616.

[0282] As silicone-based anionic hydrocarbon surfactants, Noveon (Registered Trademark) by Lubrizol Advanced Materials, Inc., SilSense TM PE-100 Silicone, SilSense TM CA-1 Silicone, and the like can be cited.

[0283] As the anionic hydrocarbon-based surfactant, sulfosuccinate surfactants such as Lankropol (registered trademark) K8300 (Akzo Nobel Surface Chemistry LLC) can be mentioned.

[0284] As the sulfosuccinate surfactant, sulfonated diisodecyl succinate Na salt, Emulsogen (registered trademark) SB10 (Clariant), sulfonated diisotridecyl succinate Na salt (Polirol (registered trademark) TR / LNA, Cesapinia Chemicals), and the like can be mentioned.

[0285] As the above hydrocarbon-based surfactant, PolyFox (registered trademark) surfactants (PolyFox TM PF-156A, PolyFox TM PF-136A, and the like) (Omnova Solutions, Inc.) can be mentioned.

[0286] As the above hydrocarbon-based surfactant, an anionic hydrocarbon-based surfactant is preferable. As the anionic hydrocarbon-based surfactant, the above-mentioned substances can be used, and for example, the following compounds can be appropriately used.

[0287] As the above anionic hydrocarbon-based surfactant, for example, the following formula (a) can be mentioned:

[0288] R 100 -COOM (a)

[0289] (in the formula, R 100 is a monovalent organic group having one or more carbon atoms. M is H, a metal atom, NR 101 4, imidazolium having or not having a substituent, pyridinium having or not having a substituent, or phosphonium having or not having a substituent, R 101 is H or an organic group, and can be the same or different). As the organic group of R 101 , an alkyl group is preferable. As R 101 , H or an organic group having 1 to 10 carbon atoms is preferable, H or an organic group having 1 to 4 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is further preferable.

[0290] From the viewpoint of the surface activity, the number of carbon atoms of R 100 is preferably two or more, and more preferably three or more. In addition, from the viewpoint of the water solubility, the number of carbon atoms of R 100 is preferably 29 or less, and more preferably 23 or less.

[0291] As the metal atom of M, an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be given, and Na, K or Li is preferable. As M, H, a metal atom or NR 101 4, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 101 4, further preferably H, Na, K, Li or NH4, further more preferably Na, K or NH4, particularly preferably Na or NH4, most preferably NH4.

[0292] As the above compound (α), a compound represented by R 102 -COOM (in the formula, R 102 is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which can have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which can have a substituent, and can contain an ether bond. In the case of 3 or more carbon atoms, a monovalent or divalent heterocycle can be contained, or a ring can be formed. M is the same as described above) can also be given.

[0293] Specifically, a compound represented by CH3-(CH2) n -COOM (in the formula, n is an integer of 2 to 28. M is the same as described above) can be given.

[0294] From the aspect of emulsion stability, the above compound (α) can not contain a carbonyl group (excluding the carbonyl group in a carboxyl group).

[0295] As the above hydrocarbon-containing surfactant not containing a carbonyl group, for example, a compound of the following formula (A) can be given:

[0296] R 103 -COO-M (A)

[0297] (in the formula, R 103 is an alkyl group, alkenyl group, alkylene group or alkenylene group having 6 to 17 carbon atoms which can contain an ether bond. M is H, a metal atom, NR 101 4, imidazolium which can have a substituent, pyridinium which can have a substituent, or phosphonium which can have a substituent. R 101 is the same or different, and is H or an organic group) can be given.

[0298] In the above formula (A), R 103 is preferably an alkyl group or alkenyl group which can contain an ether group. The alkyl group or alkenyl group in the above R 103 may be linear or branched. The number of carbon atoms of the above R 103 is not limited, and is, for example, 2 to 29.

[0299] In the case of a straight chain, the number of carbon atoms of R 103 is preferably 3 to 29, more preferably 5 to 23. In the case of a branched chain, the number of carbon atoms of R 103 is preferably 5 to 35, more preferably 11 to 23.

[0300] In the case of a straight chain, the number of carbon atoms of R 103 is preferably 2 to 29, more preferably 9 to 23. In the case of a branched chain, the number of carbon atoms of R 103 is preferably 2 to 29, more preferably 9 to 23.

[0301] As the above-mentioned alkyl group and alkenyl group, for example, a methyl group, an ethyl group, an isobutyl group, a tert-butyl group, an ethenyl group, and the like can be given.

[0302] As the above-mentioned anionic hydrocarbon-based surfactant, for example, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9, 12, 15)-linolenic acid, (6, 9, 12) linolenic acid, eleostearic acid, arachidic acid, 8, 11-eicosadienoic acid, melissic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, myricyl acid, myristoleic acid, cis-6-hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, a-eleostearic acid, β-eleostearic acid, melissic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, docosatetraenoic acid, gavacacic acid, eicosapentaenoic acid, docosapentaenoic acid, sardine acid, lignoceric acid, docosahexaenoic acid, tetracosahexaenoic acid, and salts thereof can be given.

[0303] It is particularly preferable that at least one selected from the group consisting of lauric acid, decanoic acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof.

[0304] As the above-mentioned salt, a metal atom of the above-mentioned formula M, NR 101 4, imidazolium having or not having a substituent, pyridinium having or not having a substituent, or phosphonium having or not having a substituent can be given, but is not particularly limited.

[0305] Further, as the above-mentioned anionic hydrocarbon-based surfactant, a hydrocarbon-based surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group) can be given.

[0306] As the hydrocarbon-based surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), a surfactant represented by the formula: R X -X X (in the formula, R X is a non-fluorinated organic group having 1 to 2,000 carbon atoms having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), X X is -OSO3X X1 , -COOX X1 or -SO3X X1 (X X1 is H, a metal atom, NR X1 4, imidazolium having or not having a substituent, pyridinium having or not having a substituent, or phosphonium having or not having a substituent, R X1 is H or an organic group, which can be the same or different). The carbon atom number of R X is preferably 500 or less, more preferably 100 or less, further preferably 50 or less, further more preferably 30 or less. As the organic group of R X1 , an alkyl group is preferred. As R X1 , H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms, further preferably H or an alkyl group having 1 to 4 carbon atoms.

[0307] As the above specific hydrocarbon-based surfactant, more preferably at least one selected from the group consisting of the following surfactants is used:

[0308] the following formula (a) :

[0309] [Chemical Formula 12]

[0310]

[0311] (in the formula, R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, a hydrogen atom bonded to a carbon atom can be substituted with a hydroxyl group or a monovalent organic group containing an ester bond, can contain a carbonyl group when the carbon atom number is 2 or more, and can contain a monovalent or divalent heterocycle or can form a ring when the carbon atom number is 3 or more. R 2a and R 3a are independently a single bond or a divalent linking group. R 1a , R 2a and R 3a have a total carbon atom number of 6 or more. X a is H, a metal atom, NR 4a 4, imidazolium having or not having a substituent, pyridinium having or not having a substituent, or phosphonium having or not having a substituent, R4a H or an organic group, which can be the same or different. R 1a H or an organic group, which can be the same or different. R 2a H or an organic group, which can be the same or different. R 3a Any two of R

[0312] the following formula (b) :

[0313] [Chemical Formula 13]

[0314]

[0315] (in the formula, R 1b is a linear or branched alkyl group having 1 or more carbon atoms with or without a substituent or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent, and can include a monovalent or divalent heterocycle or form a ring in the case of 3 or more carbon atoms. R 2b and R 4b independently are H or a substituent. R 3b is an alkylene group having 1 to 10 carbon atoms with or without a substituent. n is an integer of 1 or more. p and q independently are integers of 0 or more. X b is H, a metal atom, NR 5b 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 5b H or an organic group, which can be the same or different. R 1b H or an organic group, which can be the same or different. R 2b H or an organic group, which can be the same or different. R 3b H or an organic group, which can be the same or different. R 4b Any two of R 6b L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b CO-B-*, or -CO- (wherein the carbonyl group included in -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 CO-B- is excluded), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without a substituent, R 6b is H or an alkyl group having 1 to 4 carbon atoms with or without a substituent. * indicates the side to which -OSO3X b (b) represented by the following formula:

[0316] the following formula (c) :

[0317] [Chemical Formula 14]

[0318]

[0319] (In the formula, R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, a hydrogen atom bonded to a carbon atom can be substituted with a hydroxyl group or a monovalent organic group containing an ester bond, can contain a carbonyl group when the number of carbon atoms is 2 or more, and can contain a monovalent or divalent heterocycle or form a ring when the number of carbon atoms is 3 or more. R 2c and R 3c are independently a single bond or a divalent linking group. R 1c , R 2c and R 3c have a total of 5 or more carbon atoms. A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 4c is H or an organic group, which can be the same or different). R 1c , R 2c and R 3c any two of which can be bonded to each other to form a ring) ; and

[0320] the following formula (d) :

[0321] [Chemical Formula 15]

[0322]

[0323] (In the formula, R 1d is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, which can contain a monovalent or divalent heterocycle or form a ring when the number of carbon atoms is 3 or more. R 2d and R 4d are independently H or a substituent. R 3d is an alkylene group having 1 to 10 carbon atoms with or without a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. A d is -SO3X d or -COOX d (X d is H, a metal atom, NR 5d 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 5d is H or an organic group, which can be the same or different). R 1d , R2d 、R 3d and R 4d Any two of them can be bonded to each other to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*、-NR 6d CO-B-* or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6d is H or an alkyl group with 1 to 4 carbon atoms which may be substituted. * refers to the d The surfactant (d) is represented by (a) a surfactant (b) a surfactant (c) a surfactant (d ...

[0324] The surfactant (a) will be described.

[0325] In formula (a), R 1a It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0326] When the number of carbon atoms in the alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be included between two carbon atoms. Furthermore, when the number of carbon atoms in the alkyl group is 2 or more, the carbonyl group may be included at the end of the alkyl group. In other words, acyl groups such as acetyl groups represented by CH3-C(=O)- are also included in the alkyl group.

[0327] In addition, when the number of carbon atoms of the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred, for example, a furan ring, etc. 1a In the alkyl group, a divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above-mentioned alkyl group.

[0328] It should be noted that, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocyclic ring. For example, the number of carbon atoms of the group represented by CH3-C(=O)-CH2- is 3, the number of carbon atoms of the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- is 7, and the number of carbon atoms of the group represented by CH3-C(=O)- is 2.

[0329] In the above-mentioned alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0330] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 101a (Where R 101a is an alkyl group.

[0331] In the above-mentioned alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms. Preferably, the alkyl group is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0332] Where R 2a and R 3a are independently a single bond or a divalent linking group.

[0333] R 2a and R 3a Preferably, each group is independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0334] Composition R 2a and R 3a The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0335] In the above-mentioned alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0336] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 102a (Where R 102a is an alkyl group.

[0337] In the above-mentioned alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms. However, a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0338] R 1a 、R 2a and R 3a The total number of carbon atoms is 6 or more. The total number of carbon atoms is preferably 8 or more, more preferably 9 or more, further preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 15 or less.

[0339] R 1a , R 2a , and R 3a any two of which can be bonded to each other to form a ring.

[0340] In formula (a), X a is H, a metal atom, NR 4a 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 4a is H or an organic group. The four R 4a may be the same or different. As the organic group in R 4a , an alkyl group is preferred. As R 4a , H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms, further preferably H or an alkyl group having 1 to 4 carbon atoms. As the metal atom, a monovalent or divalent metal atom can be mentioned, and an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be mentioned, with Na, K, or Li being preferred.

[0341] As X a , H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 4a 4is preferred, more preferably H, Na, K, Li, or NH4for the reason of easy solubility in water, further preferably Na, K, or NH4, particularly preferably Na or NH4for the reason of more easy solubility in water, and most preferably NH4for the reason of easy removal. When X a is NH4, the above-mentioned surfactant has excellent solubility in an aqueous medium, and a metal component is not easily left in PTFE or in a final product.

[0342] As R 1a , a linear or branched alkyl group having 1 to 8 carbon atoms not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms containing a monovalent or divalent heterocycle is preferred.

[0343] Further, as R 1a , the following formula is more preferred:

[0344] [Chemical Formula 16]

[0345]

[0346] (in the formula, n 11a is an integer of 0 to 10, and R 11a is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R12a It is an alkylene group having 0 to 3 carbon atoms. 11a When R is an integer of 2 to 10, 12 (which may be the same or different).

[0347] As n 11a , preferably an integer of 0 to 5, more preferably an integer of 0 to 3, further preferably an integer of 1 to 3.

[0348] As R 11a The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0349] As R 11a In the above-mentioned alkyl group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0350] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 103a (Where R 103a is an alkyl group.

[0351] As R 11a In the above-mentioned alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but is preferably a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0352] R 12a It is an alkylene group having 0 to 3 carbon atoms, preferably 1 to 3 carbon atoms.

[0353] As R 12a The above-mentioned alkylene group may be linear or branched.

[0354] As R 12a The above alkylene group preferably does not contain a carbonyl group. 12a , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0355] As R 12a In the above-mentioned alkylene group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0356] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 104a (Where R 104a is an alkyl group.

[0357] As R 12a In the above alkylene group, 75% or less of the hydrogen atoms bonded to the carbon atom can be substituted with a halogen atom, 50% or less can be substituted with a halogen atom, and 25% or less can be substituted with a halogen atom, but it is preferable that the alkylene group not contain a halogen atom such as a fluorine atom or a chlorine atom.

[0358] As R 2a and R 3a , it is preferable that each independently be an alkylene group having 1 or more carbon atoms which does not contain a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms which does not contain a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0359] As the surfactant (a), the following surfactants can be exemplified. In each formula, X a As described above.

[0360] [Chem. 17]

[0361]

[0362] [Chem. 18]

[0363]

[0364] [Chem. 19]

[0365]

[0366] [Chem. 20]

[0367]

[0368] [Chem. 21]

[0369]

[0370] [Chem. 22]

[0371]

[0372] [Chem. 23]

[0373]

[0374] [Chem. 24]

[0375]

[0376] Next, the surfactant (b) will be described.

[0377] In formula (b), R 1ba straight-chain or branched alkyl group having 1 or more carbon atoms with or without a substituent or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent.

[0378] In the case where the number of carbon atoms of the above alkyl group is 3 or more, a monovalent or divalent heterocycle can be included or a ring can be formed. As the above heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred. Examples of the above heterocycle include a furan ring, etc. 1b In the above, a divalent heterocycle can be inserted between 2 carbon atoms, a divalent heterocycle can be located at the terminal and bonded to -C(=0)-, and a monovalent heterocycle can be located at the terminal of the above alkyl group.

[0379] Note that, in the present specification, the "number of carbon atoms" of the above alkyl group also includes the number of carbon atoms constituting the above heterocycle.

[0380] As the above alkyl group of R 1b , a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent is preferred, and a methyl group, an ethyl group, a hydroxyl group, a halogen atom, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms is particularly preferred.

[0381] As the above alkyl group of R 1b , a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent is preferred, and a methyl group, an ethyl group, a hydroxyl group, a halogen atom, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms is particularly preferred.

[0382] As the above alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted with a halogen atom, 50% or less can be substituted with a halogen atom, and 25% or less can be substituted with a halogen atom, but a non-halogenated alkyl group not including a halogen atom such as a fluorine atom or a chlorine atom is preferred.

[0383] As the above alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted with a halogen atom, 50% or less can be substituted with a halogen atom, and 25% or less can be substituted with a halogen atom, but a non-halogenated alkyl group not including a halogen atom such as a fluorine atom or a chlorine atom is preferred.

[0384] As R 1b , a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent is preferred, a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent or a cyclic alkyl group having 3 to 10 carbon atoms not including a carbonyl group is more preferred, a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent is further preferred, a straight-chain or branched alkyl group having 1 to 3 carbon atoms without a substituent is further more preferred, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0385] In formula (b), R 2b and R 4b are independently H or a substituent. Two or more of R 2b and R 4b may be the same or different.

[0386] About R 2b and R 4b The substituents are preferably halogen atoms, linear or branched alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, or hydroxyl groups, and particularly preferably methyl groups or ethyl groups.

[0387] As R 2b and R 4b The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0388] In the above alkyl group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms. However, a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0389] The above-mentioned alkyl group preferably has no substituent.

[0390] About R 2b and R 4b The above-mentioned alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, further preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not having a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0391] As R 2b and R 4b , independently preferably H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a carbonyl group, more preferably H or a straight-chain or branched alkyl group having 1 to 3 carbon atoms without a substituent, further preferably H, methyl (-CH3) or ethyl (-C2H5), and particularly preferably H.

[0392] In formula (b), R 3b It is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3b When there are two or more, they may be the same or different.

[0393] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0394] In the above-mentioned alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms. However, it is preferably a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0395] The above-mentioned alkylene group preferably has no substituent.

[0396] As the above alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms with or without a substituent or a cyclic alkylene group having 3 to 10 carbon atoms with or without a substituent is preferred, a linear or branched alkylene group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms not containing a carbonyl group is more preferred, and a linear or branched alkylene group having 1 to 10 carbon atoms without a substituent is further preferred. Examples of the above alkylene group include methylene (-CH2-), ethylene (-C2H4-), isopropylene (-CH(CH3)CH2-), and propylene (-C3H6-).

[0397] R 1b , R 2b , R 3b , and R 4b may be bonded to each other to form a ring, but it is preferred that they do not form a ring.

[0398] In formula (b), n is an integer of 1 or more. As n, an integer of 1 to 40 is preferred, an integer of 1 to 30 is more preferred, an integer of 5 to 25 is further preferred, and an integer of 5 to 9 or 11 to 25 is particularly preferred.

[0399] In formula (b), p and q are independently an integer of 0 or more. As p, an integer of 0 to 10 is preferred, and 0 or 1 is more preferred. As q, an integer of 0 to 10 is preferred, and an integer of 0 to 5 is more preferred.

[0400] n, p, and q preferably total an integer of 5 or more. The total of n, p, and q is more preferably an integer of 8 or more. The total of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and further preferably an integer of 40 or less.

[0401] In formula (b), X b is H, a metal atom, NR 5b 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 5b is H or an organic group. The four R 5b may be the same or different. As the organic group in R 5b , an alkyl group is preferred. As R 5b , H or an organic group having 1 to 10 carbon atoms is preferred, H or an organic group having 1 to 4 carbon atoms is more preferred, and H or an alkyl group having 1 to 4 carbon atoms is further preferred. As the above metal atom, monovalent and divalent metal atoms can be mentioned, and examples include alkali metals (Group 1), alkaline earth metals (Group 2), and the like, with Na, K, or Li being preferred. X b may be a metal atom or NR 5b 4(R 5b as described above).

[0402] As X b , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 5b 4, H, Na, K, Li or NH4 is more preferred due to its easy solubility in water, Na, K or NH4 is further preferred due to its easy solubility in water, Na or NH4 is particularly preferred, and NH4 is most preferred due to its easy removal. b When NH 4 is used, the surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in PTFE or the final product.

[0403] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*、-NR 6b CO-B-* or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6b is H or an alkyl group having 1 to 4 carbon atoms which may be substituted. The alkylene group more preferably has 1 to 5 carbon atoms. 6 More preferably, it is H or methyl. * refers to -OSO3X in the formula b Bonding side.

[0404] L is preferably a single bond.

[0405] As the surfactant (b), the following formula is preferred:

[0406] [Chemistry 25]

[0407]

[0408] (Where R 1b 、R 2b , L, n and X b As described above).

[0409] The surfactant (b) is 1 The integrated value of the total peak intensity observed in the chemical shift region of 2.0 to 5.0 ppm in the H-NMR spectrum is preferably 10 or more.

[0410] The surfactant (b) is 1The integral value of the total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm in the H-NMR spectrum is preferably within the above range. In this case, the above surfactant preferably has a ketone structure in the molecule.

[0411] The above integral value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and further preferably 70 or less, in the above surfactant (b).

[0412] The above integral value is measured at room temperature in a heavy water solvent. The heavy water is made to be 4.79 ppm.

[0413] As the surfactant (b), for example, the following can be given:

[0414] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0415] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0416] CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0417] CH3C(O)CH2CH2CH2CH2CH2OSO3Na,

[0418] CH3C(O)CH2CH2CH2CH2OSO3Na,

[0419] CH3C(O)CH2CH2CH2OSO3Na,

[0420] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0421] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0422] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0423] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0424] CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0425] CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na,

[0426] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na,

[0427] CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na,

[0428] CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na,

[0429] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na,

[0430] CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na,

[0431] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na,

[0432] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na,

[0433] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na,

[0434] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na,

[0435] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na,

[0436] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na,

[0437] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H,

[0438] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li,

[0439] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K,

[0440] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4,

[0441] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na,

[0442] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0443] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0444] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0445] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0446] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0447] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0448] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0449] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0450] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0451] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0452] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0453] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na,

[0454] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0455] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0456] CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0457] CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na,

[0458] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na,

[0459] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na,

[0460] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na,

[0461] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na,

[0462] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na,

[0463] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na,

[0464] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H,

[0465] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li,

[0466] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K,

[0467] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4,

[0468] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, and the like.

[0469] The surfactant (c) will be described.

[0470] In formula (c), R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0471] In the case where the above alkyl group has 3 or more carbon atoms, a carbonyl group (-C(=O)-) can be included between 2 carbon atoms. In the case where the above alkyl group has 2 or more carbon atoms, the above carbonyl group can also be included at the terminal of the above alkyl group. That is, acyl groups such as acetyl group represented by CH3-C(=O)- are also included in the above alkyl group.

[0472] In addition, when the number of carbon atoms of the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. As the heterocyclic ring, an unsaturated heterocyclic ring is preferred, and an oxygen-containing unsaturated heterocyclic ring is more preferred, for example, a furan ring, etc. 1c In the alkyl group, a divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above-mentioned alkyl group.

[0473] It should be noted that, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocyclic ring. For example, the number of carbon atoms of the group represented by CH3-C(=O)-CH2- is 3, the number of carbon atoms of the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- is 7, and the number of carbon atoms of the group represented by CH3-C(=O)- is 2.

[0474] In the above-mentioned alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0475] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 101c (Where R 101c is an alkyl group.

[0476] In the above alkyl group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms. However, a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0477] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group.

[0478] R 2c and R 3c Each of the groups is independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0479] Composition R 2c and R 3c The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0480] In the above-mentioned alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0481] As the monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 102c (in the formula, R 102c is an alkyl group) can be given.

[0482] In the above alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted with halogen atoms, 50% or less can be substituted with halogen atoms, and 25% or less can be substituted with halogen atoms, but a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0483] R 1c , R 2c , and R 3c The total number of carbon atoms of R 1c , R 2c , and R 3c is 5 or more. As the total number of carbon atoms, 7 or more, more preferably 9 or more, and preferably 20 or less, more preferably 18 or less, and further preferably 15 or less are preferred.

[0484] R 1c , R 2c , and R 3c is 5 or more. As the total number of carbon atoms, 7 or more, more preferably 9 or more, and preferably 20 or less, more preferably 18 or less, and further preferably 15 or less are preferred.

[0485] In formula (c), A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an imidazolium having or not having a substituent, a pyridinium having or not having a substituent, or a phosphonium having or not having a substituent, R 4c is H or an organic group, which can be the same or different). As the organic group in R 4c , an alkyl group is preferred. As R 4c , H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. As the above metal atom, monovalent and divalent metal atoms can be given, and an alkali metal (Group 1), an alkaline earth metal (Group 2), and the like can be given, and Na, K, or Li is preferred.

[0486] As X c , H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 4c 4is more preferred, Na, K, Li, or NH4is further preferred for easier solubility in water, Na, K, or NH4, particularly Na or NH4is especially preferred, and NH4is most preferred for easier removal. X cWhen NH4, the above surfactant has excellent solubility in an aqueous medium and is not likely to leave a metal component in PTFE or in a final product.

[0487] R as R 1c , a linear or branched alkyl group having 1 to 8 carbon atoms not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms containing a carbonyl group, or an alkyl group having 1 or 2 valent heterocycles having 3 to 45 carbon atoms.

[0488] In addition, as R 1c , the following formula is more preferable:

[0489] [Chemical Formula 26]

[0490]

[0491] (In the formula, n 11c is an integer of 0 to 10, R 11c is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R 12c is an alkylene group having 0 to 3 carbon atoms. When n 11c is an integer of 2 to 10, R 12c may be the same or different, respectively).

[0492] As n 11c , an integer of 0 to 5 is preferable, an integer of 0 to 3 is more preferable, and an integer of 1 to 3 is further preferable.

[0493] The above alkyl group as R 11c preferably does not contain a carbonyl group.

[0494] In the above alkyl group as R 11c , a hydrogen atom bonded to a carbon atom can be substituted with a functional group, such as a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0495] As the above monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 103c (In the formula, R 103c is an alkyl group) can be given.

[0496] In the above alkyl group as R 11c , 75% or less of hydrogen atoms bonded to carbon atoms can be substituted with halogen atoms, 50% or less can be substituted with halogen atoms, and 25% or less can be substituted with halogen atoms, but a non-halogenated alkyl group not containing halogen atoms such as a fluorine atom and a chlorine atom is preferable.

[0497] R 12c It is an alkylene group having 0 to 3 carbon atoms, preferably 1 to 3 carbon atoms.

[0498] As R 12c The above-mentioned alkylene group may be linear or branched.

[0499] As R 12c The above alkylene group preferably does not contain a carbonyl group. 12c , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0500] As R 12c In the above-mentioned alkylene group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0501] Examples of the monovalent organic group containing an ester bond include the group of formula: -OC(=O)-R 104c (Where R 104c is an alkyl group.

[0502] As R 12c In the above-mentioned alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but is preferably a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0503] As R 2c and R 3c , are independently preferably an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0504] Examples of the surfactant (c) include the following surfactants. c As mentioned above.

[0505] [Chemistry 27]

[0506]

[0507] [Chemistry 28]

[0508]

[0509] [Chemistry 29]

[0510]

[0511] [Chemical Formula 30]

[0512]

[0513] [Chemical Formula 31]

[0514]

[0515] [Chemical Formula 32]

[0516]

[0517] [Chemical Formula 33]

[0518]

[0519] [Chemical Formula 34]

[0520]

[0521] The surfactant (d) will be described.

[0522] In the formula (d), R 1d is a linear or branched alkyl group having 1 or more carbon atoms, or a cyclic alkyl group having 3 or more carbon atoms, with or without a substituent.

[0523] In the case where the number of carbon atoms of the above alkyl group is 3 or more, a monovalent or divalent heterocycle can be included, or a ring can be formed. As the above heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred, and examples thereof include a furan ring, etc. R 1d In the formula (d), a divalent heterocycle can be inserted between 2 carbon atoms, a divalent heterocycle can be located at the terminal and bonded to -C(=0)-, and a monovalent heterocycle can be located at the terminal of the above alkyl group.

[0524] Note that, in the present specification, the "number of carbon atoms" of the above alkyl group also includes the number of carbon atoms constituting the above heterocycle.

[0525] As the above alkyl group for R 1d , a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, a hydroxyl group, a halogen atom, and the like can be included as a substituent. Preferably, a methyl group, an ethyl group, and the like are included.

[0526] As the above alkyl group for R 1d , a carbonyl group is preferably not included.

[0527] In the above alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted with a halogen atom, 50% or less can be substituted with a halogen atom, and 25% or less can be substituted with a halogen atom, but a non-halogenated alkyl group not including a halogen atom such as a fluorine atom or a chlorine atom is preferred.

[0528] The above alkyl group preferably has no substituent.

[0529] As R 1d , a linear or branched alkyl group having or not having a substituent and having 1 to 10 carbon atoms or a cyclic alkyl group having or not having a substituent and having 3 to 10 carbon atoms are preferable, a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group are more preferable, a linear or branched alkyl group having 1 to 10 carbon atoms not having a substituent is further preferable, a linear or branched alkyl group having 1 to 3 carbon atoms not having a substituent is further more preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable, and a methyl group (-CH3) is most preferable.

[0530] In formula (d), R 2d and R 4d are independently H or a substituent. Two or more of R 2d and R 4d may be the same or different.

[0531] As R 2d and R 4d , a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a hydroxyl group are preferable, and a methyl group, an ethyl group are particularly preferable.

[0532] As R 2d and R 4d , the above alkyl group preferably does not contain a carbonyl group.

[0533] In the above alkyl group, 75% or less of hydrogen atoms bonded to carbon atoms can be substituted with a halogen atom, 50% or less of hydrogen atoms bonded to carbon atoms can be substituted with a halogen atom, and 25% or less of hydrogen atoms bonded to carbon atoms can be substituted with a halogen atom, but a non-halogenated alkyl group not containing a halogen atom such as a fluorine atom or a chlorine atom is preferable.

[0534] The above alkyl group preferably has no substituent.

[0535] As R 2d and R 4d , a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group are preferable, a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms not having a substituent is further preferable, and a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferable.

[0536] As R 2d and R 4d, independently preferably H or a linear or branched alkyl group having 1 to 10 carbon atoms without a carbonyl group, more preferably H or a linear or branched alkyl group having 1 to 3 carbon atoms without a substituent, further preferably H, methyl (-CH3) or ethyl (-C2H5), and particularly preferably H.

[0537] In formula (d), R 3d It is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3d When there are two or more, they may be the same or different.

[0538] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0539] In the above-mentioned alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms. However, it is preferably a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0540] The above-mentioned alkylene group preferably has no substituent.

[0541] As the above-mentioned alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted or an cyclic alkylene group having 3 to 10 carbon atoms which may be substituted or an unsubstituted group is preferred. A linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group or an cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group is preferred. A linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a substituent is more preferred. A methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylidene group (-CH(CH3)CH2-) or a propylene group (-C3H6-) is further preferred.

[0542] R 1d 、R 2d 、R 3d and R 4d Any two of them may be bonded to each other to form a ring.

[0543] In formula (d), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and even more preferably an integer of 5 to 25.

[0544] In formula (d), p and q are independently an integer greater than 0. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0545] n, p and q are preferably an integer of 6 or more. The sum of n, p and q is more preferably an integer of 8 or more. The sum of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and further preferably an integer of 40 or less.

[0546] In formula (d), A d is -SO3X d or -COOX d (X d is H, a metal atom, NR 5d 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 5d is H or an organic group, which can be the same or different). As the organic group in R 5d , an alkyl group is preferred. As R 5d , H or an organic group having 1 to 10 carbon atoms is preferred, and more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. As the above metal atom, monovalent and divalent metal atoms can be mentioned, and alkali metals (Group 1), alkaline earth metals (Group 2), etc. can be mentioned, and Na, K or Li is preferred. X d may be a metal atom or NR 5d 4(R 5d as described above).

[0547] As X d , H, alkali metals (Group 1), alkaline earth metals (Group 2) or NR 5d 4is preferred, and for the reason of easy solubility in water, H, Na, K, Li or NH4is more preferred, and for the reason of further easy solubility in water, Na, K or NH4, and particularly Na or NH4is further preferred, and for the reason of easy removal, NH4is most preferred. When X d is NH4, the above surfactant has excellent solubility in an aqueous medium, and a metal component is not easily left in PTFE or in a final product.

[0548] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (in which -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B- containing a carbonyl group), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms with or without a substituent. The above alkylene group is more preferably an alkylene group having 1 to 5 carbon atoms. In addition, the above R6d More preferably, H or methyl. * means the side bonded to A d in the formula.

[0549] L is preferably a single bond.

[0550] The above-mentioned surfactant preferably has a total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm in the H-NMR spectrum of 10 or more. 1 The integral value of the total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm in the H-NMR spectrum is preferably 10 or more.

[0551] The above-mentioned surfactant preferably has a total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm in the H-NMR spectrum of 10 or more. 1 The integral value of the total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm in the H-NMR spectrum is preferably within the above-mentioned range. In this case, the above-mentioned surfactant preferably has a ketone structure in the molecule.

[0552] The above-mentioned integral value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and further preferably 70 or less.

[0553] The above-mentioned integral value is measured in a heavy water solvent at room temperature. The heavy water is 4.79 ppm.

[0554] As the above-mentioned surfactant (d), for example, the following substances can be mentioned:

[0555] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK,

[0556] CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa,

[0557] CH3C(O)CH2CH2CH2CH2CH2CH2COONa,

[0558] CH3C(O)CH2CH2CH2CH2CH2COONa,

[0559] CH3C(O)CH2CH2CH2CH2COONa,

[0560] CH3C(O)CH2CH2CH2COONa,

[0561] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[0562] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[0563] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[0564] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[0565] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[0566] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa,

[0567] CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa,

[0568] CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa,

[0569] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa,

[0570] CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa,

[0571] CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa,

[0572] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa,

[0573] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa,

[0574] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK,

[0575] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK,

[0576] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa,

[0577] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa,

[0578] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa,

[0579] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH,

[0580] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi,

[0581] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4,

[0582] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa,

[0583] CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK,

[0584] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0585] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0586] CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na,

[0587] CH3C(O)CH2CH2CH2CH2CH2SO3Na,

[0588] CH3C(O)CH2CH2CH2CH2SO3Na,

[0589] CH3C(O)CH2CH2CH2SO3Na,

[0590] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0591] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0592] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0593] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0594] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0595] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0596] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0597] CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na,

[0598] CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na,

[0599] CH3C(O)CH2CH2CH2CH2CH2SO3Na,

[0600] CH3C(O)CH2CH2CH2CH2SO3Na,

[0601] CH3C(O)CH2CH2CH2SO3Na,

[0602] CH3C(O)CH2CH2SO3Na,

[0603] CH3C(O)CH2SO3Na,

[0604] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na,

[0605] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na,

[0606] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na,

[0607] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na,

[0608] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na,

[0609] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na,

[0610] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H,

[0611] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K,

[0612] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li,

[0613] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4,

[0614] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na.

[0615] As the above-mentioned anionic hydrocarbon-based surfactant, a surfactant represented by the following general formula (1-0) (hereinafter also referred to as surfactant (1)) can be given:

[0616] General formula (1-0):

[0617] [Chemical Formula 35]

[0618]

[0619] (In the formula, R 1 ~R 5 represents H or a monovalent substituent, wherein at least one of R 1 and R 3 represents a group represented by the general formula: -Y-R 6 and at least one of R 2 and R 5 represents a group represented by the general formula: -X-A or a group represented by the general formula: -Y-R 6

[0620] In addition, X is the same or different at each occurrence and represents a divalent linking group or a bond;

[0621] A is the same or different at each occurrence and represents -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7 4) imidazolium having or not having a substituent, pyridinium having or not having a substituent, or phosphonium having or not having a substituent (R 7 is H or an organic group); ​

[0622] Y represents, at each occurrence, a divalent linking group selected from the group consisting of -S(=0)2-, -0-, -COO-, -OCO-, -CONR 8 - and -NR 8 CO-, or a bond, R 8 is H or an organic group;

[0623] R 6 represents, at each occurrence, an alkyl group having 2 or more carbon atoms which can contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms.

[0624] R 1 ~R 5 , any two of which can be bonded to each other to form a ring.

[0625] The surfactant (1) will be described.

[0626] in the formula, R 1 ~R 5 represents H or a monovalent substituent, wherein R 1 and at least one of R 3 represents a group represented by the general formula: -Y-R 6 and at least one of R 2 and R 5 represents a group represented by the general formula: -X-A or a group represented by the general formula: -Y-R 6 R 1 ~R 5 , any two of which can be bonded to each other to form a ring.

[0627] As the above-mentioned substituents which the above-mentioned alkyl group as R 1 may have, halogen atoms, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, or cyclic alkyl groups having 3 to 10 carbon atoms, a hydroxyl group are preferred, and methyl groups, ethyl groups are particularly preferred.

[0628] The above-mentioned alkyl group as R 1 preferably does not contain a carbonyl group.

[0629] In the above-mentioned alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted with halogen atoms, 50% or less of the hydrogen atoms bonded to carbon atoms can be substituted with halogen atoms, 25% or less of the hydrogen atoms bonded to carbon atoms can be substituted with halogen atoms, but a non-halogenated alkyl group which does not contain halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0630] The above-mentioned alkyl group preferably does not have any substituents.

[0631] The above-mentioned alkyl group as R 1, preferably a linear or branched alkyl group having or not having a substituent and having 1 to 10 carbon atoms, or a cyclic alkyl group having or not having a substituent and having 3 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group, further preferably a linear or branched alkyl group having 1 to 10 carbon atoms not having a substituent, further more preferably a linear or branched alkyl group having 1 to 3 carbon atoms not having a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), most preferably a methyl group (-CH3).

[0632] As a monovalent substituent, a group represented by the general formula: -Y-R 6 , a group represented by the general formula: -X-A, -H, a C 1-20 alkyl group having or not having a substituent, -NH2, -NHR 9 (R 9 is an organic group), -OH, -COOR 9 (R 9 is an organic group), or -OR 9 (R 9 is an organic group). The number of carbon atoms of the above alkyl group is preferably 1 to 10.

[0633] As R 9 , a C 1-10 alkyl group or a C 1-10 alkylcarbonyl group is preferred, and a C 1-4 alkyl group or a C 1-4 alkylcarbonyl group is more preferred.

[0634] In the formula, X is the same or different at each occurrence and represents a divalent linking group or a bond.

[0635] R 6 In the case where R 8 does not contain any one of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X is preferably a divalent linking group containing at least one bond selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0636] As X, a divalent linking group containing at least one bond selected from the group consisting of -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -O-S(=O)2-, -CONR 8 -, and -NR 8 CO- is preferred, a C 1-10 alkylene group or a bond is more preferred. R 8 represents H or an organic group.

[0637] As the organic group in R 8 , an alkyl group is preferred. As the organic group in R8 H or an organic group, more preferably H or an organic group of C 1-10 H or an organic group, more preferably H or an organic group of C 1-4 H or an organic group, more preferably H or an organic group of C 1-4 H or an alkyl group, further more preferably H.

[0638] In the formula, A is the same or different at each occurrence and represents -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7 4, imidazolium with or without a substituent, pyridinium with or without a substituent, or phosphonium with or without a substituent, R 7 is H or an organic group. The 4 R 7 may be the same or different.

[0639] As the organic group in R 7 , an alkyl group is preferred. As R 7 , H or an organic group of C 1-10 is preferred, more preferably H or an organic group of C 1-4 is preferred, further preferably H or an organic group of C 1-4 H or an alkyl group is preferred.

[0640] As the metal atom, an alkali metal (Group 1), an alkaline earth metal (Group 2) or the like can be given, with Na, K or Li being preferred.

[0641] As M, H, a metal atom or NR 7 4 is preferred, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4 is preferred, further preferably H, Na, K, Li or NH4, further more preferably Na, K or NH4, particularly preferably Na or NH4, most preferably NH4.

[0642] In the formula, Y is the same or different at each occurrence and represents a divalent linking group selected from the group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 CO-, or a bond, R 8 represents H or an organic group.

[0643] As Y, a bond, a divalent linking group selected from the group consisting of -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 CO- is preferred, more preferably a bond, a divalent linking group selected from the group consisting of -COO- and -OCO-.

[0644] As the organic group in R 8 , an alkyl group is preferred. As R 8 , H or an organic group of C1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 The alkyl group is more preferably H.

[0645] Where R 6 The same or different at each occurrence, represents an alkyl group having 2 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms. 6 The number of carbon atoms in the organic group is preferably 2-20, more preferably 2-10.

[0646] R 6 The alkyl group may contain one or more carbonyl groups, ester groups, amide groups and sulfonyl groups between carbon atoms, and these groups are not contained at the terminal of the alkyl group. 6 In the alkyl group, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0647] As R 6 , preferably:

[0648] General formula: -R 10 -CO-R 11 The groups represented

[0649] General formula: -R 10 -COO-R 11 The groups represented

[0650] General formula: -R 11 The groups represented

[0651] General formula: -R 10 -NR 8 CO-R 11 The group represented, or

[0652] General formula: -R 10 -CONR 8 -R 11 The group represented

[0653] (Where R 8 Represents H or an organic group. 10 is an alkylene group, R 11 is an alkyl group which may have a substituent).

[0654] As R 6 , more preferably the general formula: -R 10-CO-R 11 The group represented.

[0655] As R 8 The organic group in is preferably an alkyl group. 8 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 The alkyl group is more preferably H.

[0656] R 10 The number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. 10 The number of carbon atoms in the alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 3-10.

[0657] R 11 The number of carbon atoms in the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10, further more preferably 1 to 8, particularly further preferably 1 to 6, still further preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. 11 The alkyl group of R is preferably composed of only primary carbon, secondary carbon and tertiary carbon, and is particularly preferably composed of only primary carbon and secondary carbon. 11 , preferably methyl, ethyl, n-propyl, isopropyl, and most preferably methyl.

[0658] As the surfactant (1), a compound represented by the general formula (1-1), a compound represented by the general formula (1-2), or a compound represented by the general formula (1-3) is preferred, and a compound represented by the general formula (1-1) or a compound represented by the general formula (1-2) is more preferred.

[0659] General formula (1-1):

[0660] [Chemistry 36]

[0661]

[0662] (Where R 3 ~R 6 , X, A and Y as described above)

[0663] General formula (1-2):

[0664] [Chemistry 37]

[0665]

[0666] (Where R 4~R 6 X, A and Y are as described above

[0667] General formula (1-3):

[0668] [Chem. 38]

[0669]

[0670] (in the formula, R 2 R 4 ~R 6 X, A and Y are as described above

[0671] As the group represented by the general formula: -X-A, preferably

[0672] -COOM,

[0673] -R 12 COOM,

[0674] -SO3M,

[0675] -OSO3M,

[0676] -R 12 SO3M,

[0677] -R 12 OSO3M,

[0678] -OCO-R 12 -COOM,

[0679] -OCO-R 12 -SO3M,

[0680] -OCO-R 12 -OSO3M,

[0681] -COO-R 12 -COOM,

[0682] -COO-R 12 -SO3M,

[0683] -COO-R 12 -OSO3M,

[0684] -CONR 8 -R 12 -COOM,

[0685] -CONR 8 -R 12 -SO3M,

[0686] -CONR 8 -R 12 -OSO3M,

[0687] -NR 8 CO-R 12 -COOM,

[0688] -NR 8 CO-R 12 -SO3M,

[0689] -NR 8 CO-R 12 -OSO3M,

[0690] -OS(=O)2-R 12 -COOM,

[0691] -OS(=O)2-R 12 -SO3M, or

[0692] -OS(=O)2-R 12 -OSO3M

[0693] (Where R 8 and M as above. R 12 C 1-10 alkylene).

[0694] The above R 12 In the alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but is preferably a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0695] As a general formula: -YR 6 The group represented by

[0696] General formula: -R 10 -CO-R 11 The groups represented

[0697] General formula: -OCO-R 10 -CO-R 11 The groups represented

[0698] General formula: -COO-R 10 -CO-R 11 The groups represented

[0699] General formula: -OCO-R 10 -COO-R 11 The groups represented

[0700] General formula: -COO-R 11 The groups represented

[0701] General formula: -NR 8 CO-R 10 -CO-R 11 the group represented by

[0702] General formula: -CONR 8 -R 10 -NR 8 CO-R 11 the group represented by

[0703] (in the formula, R 8 , R 10 , and R 11 are as described above).

[0704] (in the formula, R 4 and R 5 are preferably independently H or C 1-4 alkyl.

[0705] In the above-mentioned alkyl group of R 4 and R 5 , 75% or less of the hydrogen atoms bonded to the carbon atom can be substituted with halogen atoms, 50% or less can be substituted with halogen atoms, and 25% or less can be substituted with halogen atoms, but it is preferable that the alkyl group not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0706] As R 3 in General Formula (1-1), H or C 1-20 alkyl with or without a substituent is preferable, C 1-20 alkyl without a substituent is more preferable, and H is further preferable.

[0707] In the above-mentioned alkyl group of R 3 , 75% or less of the hydrogen atoms bonded to the carbon atom can be substituted with halogen atoms, 50% or less can be substituted with halogen atoms, and 25% or less can be substituted with halogen atoms, but it is preferable that the alkyl group not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0708] As R 2 in General Formula (1-3), H, OH, or C 1-20 alkyl with or without a substituent is preferable, C 1-20 alkyl without a substituent is more preferable, and H or OH is further preferable.

[0709] In the above-mentioned alkyl group of R 2 , 75% or less of the hydrogen atoms bonded to the carbon atom can be substituted with halogen atoms, 50% or less can be substituted with halogen atoms, and 25% or less can be substituted with halogen atoms, but it is preferable that the alkyl group not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0710] Examples of the anionic hydrocarbon surfactant include the following formula (1-0A):

[0711] [Chemistry 39]

[0712]

[0713] (Where R 1A ~R 5A H, a monovalent hydrocarbon group which may contain an ester group between carbon atoms, or a general formula: -X A -A represented by the group. 2A and R 5A At least one of them represents the general formula: -X A -The group represented by A.

[0714] X A The same or different at each occurrence, a divalent hydrocarbon group or a bond;

[0715] A is the same or different at each occurrence, and is -COOM (M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group);

[0716] R 1A ~R 5A Any two of them may be bonded to each other to form a ring) and the like.

[0717] In the general formula (1-0A), R 1A ~R 5A The number of carbon atoms in the monovalent hydrocarbon group which may contain an ester group between carbon atoms is preferably 1 to 50, more preferably 5 to 20. 1A ~R 5A Any two of them may be bonded to each other to form a ring. As the monovalent hydrocarbon group which may contain an ester group between carbon atoms, an alkyl group is preferable.

[0718] Where, X A The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 50, more preferably 5 to 20. Examples of the divalent hydrocarbon group include an alkylene group and an alkanediyl group, and an alkylene group is preferred.

[0719] In the general formula (1-0A), preferably R 2A and R 5A Any one of the above general formula: -X A -A, more preferably R 2A For the above general formula: -XA a group represented by -A.

[0720] In General Formula (1-0A), as a suitable mode, the following mode is preferable: R 2A is a general formula: -X A a group represented by -A, R 1A , R 3A , R 4A and R 5A is H. In this case, X A is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0721] In General Formula (1-0A), as a suitable mode, the following mode is preferable: R 2A is a general formula: -X A a group represented by -A, R 1A and R 3A is -Y A -R 6 a group represented by -A, Y A is, at each occurrence, independently -COO-, -OCO-, or a bond, R 6 is, at each occurrence, independently an alkyl group having 2 or more carbon atoms. In this case, R 4A and R 5A is preferably H.

[0722] As the hydrocarbon-based surfactant represented by General Formula (1-0A), for example, glutaric acid or a salt thereof, adipic acid or a salt thereof, pimelic acid or a salt thereof, suberic acid or a salt thereof, azelaic acid or a salt thereof, sebacic acid or a salt thereof, and the like can be given.

[0723] In addition, the carboxylic acid-type hydrocarbon-based surfactant of the aliphatic type represented by General Formula (1-0A) can be a synthetic surfactant of a double-chain amphiphilic group type, and, for example, as a gemini-type surfactant, Geminisurf (Nikkol Co., Ltd.), Gemsurf α 142 (lauric acid group having 12 carbon atoms), Gemsurf α 102 (having 10 carbon atoms), Gemsurf α 182 (having 14 carbon atoms), and the like can be given.

[0724] The above hydrocarbon-based surfactant can be subjected to radical treatment or oxidation treatment.

[0725] The radical treatment is a treatment for generating radicals in the hydrocarbon surfactant, and for example, the following treatment is performed: deionized water and the hydrocarbon surfactant are added to a reactor, the reactor is closed, the inside of the system is replaced with nitrogen, the reactor is heated and pressurized, a polymerization initiator is then added, the reactor is stirred for a certain period of time, and then the reactor is depressurized until atmospheric pressure is reached, and then the reactor is cooled. The oxidation treatment is a treatment for adding an oxidizing agent to the hydrocarbon surfactant. As the oxidizing agent, for example, oxygen, ozone, hydrogen peroxide, manganese (IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, and the like can be given.

[0726] In the production method of the present application, two or more of the above hydrocarbon surfactants can be used simultaneously.

[0727] In the production method of the present application, the polymerization step can be performed in the presence of a nonionic surfactant not containing a fluorine atom. As the nonionic surfactant, at least one selected from the group consisting of:

[0728] General Formula (250): H(OR 251 ) u (OR 252 ) v OH

[0729] (In the formula, R 251 and R 252 are alkylene groups having 1 to 4 carbon atoms, and u and v are integers of 1 to 5. Among them, R 251 is different from R 252 ) ;

[0730] a nonionic surfactant having a hydrophobic group composed of a hydrocarbon group having 8 to 20 carbon atoms and a hydrophilic group composed of a polyalkylene oxide in the molecule; and

[0731] General Formula (260): R 261 m -Si-(OR 262 ) 4-m

[0732] (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).

[0733] As the block polymer represented by General Formula (250), if specific examples are given, a block polymer composed of at least two segments selected from the group consisting of polyoxyethylene, polyoxypropylene, and polyoxybutylene can be exemplified. Among them, a polyoxyethylene-polyoxypropylene block polymer, a polyoxyethylene-polyoxybutylene block polymer can be exemplified, not only a block polymer of the A-B type can be preferably exemplified, but also a block polymer of the A-B-A type can be preferably exemplified. It is further preferable that a stable dispersion liquid of a fluorine-containing polymer can be prepared at a high concentration by using a polyoxyethylene-polyoxypropylene block polymer, a polyoxypropylene-polyoxyethylene-polyoxypropylene block polymer. In addition, when the content of the polyoxyethylene segment is 10 to 50%, it is considered that the generation of aggregates due to re-aggregation is small, and thus it is preferable; further, when the content is 20 to 40%, a dispersion liquid of a fluorine-containing polymer having low viscosity can be prepared, and thus it is preferable. The molecular weight is not particularly limited, and it is only necessary to be 1000 to 7000 g / mol, and further particularly when the molecular weight is 2500 to 6500 g / mol, a dispersion liquid having low viscosity and excellent dispersibility can be prepared.

[0734] As the above-mentioned surfactant, a compound not containing a perfluoroalkyl group having 3 or more carbon atoms is preferable. Specifically, a compound not containing a perfluoroalkyl group having 3 or more carbon atoms among the above-mentioned hydrocarbon surfactants and the above-mentioned fluorine-containing surfactants can be exemplified.

[0735] As the above-mentioned surfactant, a compound not containing a perfluoroalkyl group having 2 or more carbon atoms is more preferable, a compound not containing a perfluoroalkyl group having 1 or more carbon atoms is further preferable, and a compound not containing a fluorine atom is further more preferable.

[0736] In the production method of the present application, the method in which the surfactant is a hydrocarbon surfactant is one of suitable methods. In the case of producing a fluorine-containing polymer having many TFE units, if a hydrocarbon surfactant is used, there is a problem that the molecular weight is difficult to increase, and generally, a chain transfer agent which decreases the molecular weight of the obtained polymer is not used. In the production method of the present application, it has been surprisingly found that even in the case of producing a fluorine-containing polymer having many TFE units using a hydrocarbon surfactant, polymerization can be efficiently performed, and thus the production method of the present application has been completed.

[0737] The above hydrocarbon-based surfactant is preferably a hydrocarbon-based surfactant of anionic type, more preferably at least one selected from the group consisting of the above compound (a), the above surfactant (a), the above surfactant (b), the above surfactant (c), the above surfactant (d), the above surfactant (1), and the above surfactant (1-0A), and a substance obtained by subjecting these surfactants to radical treatment or oxidation treatment, further preferably at least one selected from the group consisting of the above compound (a), the above surfactant (b), the above surfactant (d), the above surfactant (1), and a substance obtained by subjecting these surfactants to radical treatment or oxidation treatment, particularly preferably at least one selected from the group consisting of the above compound (a) and the above surfactant (b).

[0738] The above surfactant can be added in the form of an aqueous solution containing water. The upper limit of the concentration of the above surfactant in the above aqueous solution is preferably 50% by mass, more preferably 30% by mass, further preferably 20% by mass, further more preferably 100,000 ppm, still further preferably 50,000 ppm, particularly preferably 10,000 ppm, most preferably 5,000 ppm. The lower limit is preferably 1 ppm, more preferably 10 ppm, further preferably 50 ppm.

[0739] The above surfactant is preferably a polymerization surfactant used for the production of a fluorine-containing polymer, or an aqueous solution of a polymerization surfactant used for the production of a fluorine-containing polymer.

[0740] In the production method of the present application, the above surfactant can be added to the above aqueous medium before the start of the polymerization reaction, or can be added at the start of the polymerization reaction, or can be added after the start of the polymerization reaction.

[0741] From the viewpoint of promoting the polymerization of a fluorine-containing monomer and obtaining a fluorine-containing polymer having a higher molecular weight, it is preferable that the surfactant be substantially not added before the start of the polymerization reaction, and be added after the start of the polymerization reaction.

[0742] It is more preferable that the above surfactant be substantially not added until the end of the initial period during which an initial dispersion of fluorine-containing polymer particles in the above aqueous medium is prepared (hereinafter also referred to as an initial period), and be added after the initial period.

[0743] At the start of the polymerization reaction (preferably in the above initial period), the content of the above surfactant in the above aqueous medium is, for example, preferably 50 ppm or less, more preferably 40 ppm or less, further preferably 30 ppm or less, further more preferably 20 ppm or less, particularly preferably 15 ppm or less, relative to the above aqueous medium.

[0744] The content of the surfactant in the aqueous medium at the start of the polymerization, preferably during the initial period described above, is preferably 50 ppm or less, more preferably 40 ppm or less, further preferably 30 ppm or less, further more preferably 20 ppm or less, particularly preferably 15 ppm or less, most preferably 5 ppm or less, based on the aqueous medium.

[0745] The concentration of the fluoropolymer in the aqueous medium at the time of starting the addition of the surfactant is preferably 0.6% by mass or more, more preferably 0.7% by mass or more, further preferably 0.8% by mass or more, further more preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, based on the aqueous medium.

[0746] When the fluoropolymer is a melt-processable fluororesin (e.g., FEP, PFA) described later, the concentration is preferably 2.0% by mass or more.

[0747] When the fluoropolymer is a non-melt-processable fluororesin (e.g., PTFE) described later, the concentration is preferably 1.0% by mass or more, more preferably 1.6% by mass or more.

[0748] When the surfactant is added to the aqueous medium, the supply rate is preferably 0.005 to 1.4 g / l-h, more preferably 0.005 to 1.0 g / l-h, further preferably 0.01 to 0.8 g / l-h.

[0749] In the unit g / l-h, "g" indicates the mass of the surfactant itself, "l" indicates the volume of the polymerization reactor, and "h" indicates time.

[0750] The addition of the surfactant is preferably performed at least every 20 minutes, more preferably at least every 10 minutes, further preferably at least every 5 minutes, most preferably continuously until the end of the polymerization.

[0751] The polymerization process is a process for obtaining a fluoropolymer containing more than 80 mol% of polymer units based on TFE (hereinafter also referred to as "TFE units").

[0752] The fluoropolymer obtained by the above polymerization step may contain more than 80 mol% of TFE units and may be a homopolymer of TFE or a polymer containing more than 80 mol% of TFE units and less than 20 mol% of polymerized units derived from monomers other than TFE. The above fluoropolymer preferably contains more than 90 mol% of TFE units. The above fluoropolymer is preferably a TFE homopolymer composed solely of TFE units, and preferably contains less than 20 mol%, more preferably less than 10 mol%, of polymerized units derived from monomers other than TFE.

[0753] The monomer other than TFE may be a fluorine-containing monomer containing a fluorine atom or a non-fluorine-containing monomer.

[0754] The fluorinated monomer preferably has at least one double bond.

[0755] The fluorinated monomer is preferably selected from hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkylethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutylene, hexafluoroisobutylene, the general formula (100): CH2=CFRf 101 (Where Rf 101 At least one member selected from the group consisting of a fluorinated monomer represented by a linear or branched fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated vinyl heterocyclic compound, a fluorinated methylenedioxolane, a monomer providing a crosslinking site, and a fluorinated acrylate monomer.

[0756] As the fluoroalkyl vinyl ether, for example, at least one selected from the group consisting of the following substances is preferred:

[0757] General formula (110): CF2=CF-ORf 111

[0758] (Where Rf 111 represents a perfluorinated organic group);

[0759] General formula (120): CF2=CF-OCH2-Rf 121

[0760] (Where Rf 121 A fluorinated monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms;

[0761] General formula (130): CF2=CFOCF2ORf 131

[0762] (Where Rf 131A fluorinated monomer represented by a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms;

[0763] General formula (140): CF2=CFO(CF2CF(Y 141 )O) m (CF2) n F

[0764] (Where Y 141 represents a fluorine atom or a trifluoromethyl group. m is an integer from 1 to 4. n is an integer from 1 to 4); and

[0765] General formula (150): CF2=CF-O-(CF2CFY 151 -O) n -(CFY 152 ) m -A 151

[0766] (Where Y 151 represents a fluorine atom, a chlorine atom, a -SO2F group or a perfluoroalkyl group. The perfluoroalkyl group may contain an ethereal oxygen and a -SO2F group. n represents an integer from 0 to 3. n Y 151 Can be the same or different. 152 represents a fluorine atom, a chlorine atom or a -SO2F group. m represents an integer from 1 to 5. m Y 152 Can be the same or different. 151 Indicates -SO2X 151 、-COZ 151 or-POZ 152 Z 153 .X 151 Indicates F, Cl, Br, I, -OR 151 or -NR 152 R 153 . Z 151 , Z 152 and Z 153 Same or different, indicates -NR 154 R 155 OR 156 . R 151 、R 152 、R 153 、R 154 、R 155 and R 156 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 group-containing group).

[0767] In the present specification, the above-mentioned "perfluoro organic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The above-mentioned perfluoro organic group can have an ether oxygen.

[0768] As the fluorine-containing monomer represented by General Formula (110), Rf 111 is a fluorine-containing monomer in which Rf is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

[0769] As the perfluoro organic group in General Formula (110), for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, or the like can be mentioned.

[0770] As the fluorine-containing monomer represented by General Formula (110), the following fluorine-containing monomers can also be mentioned:

[0771] In the above-mentioned General Formula (110),

[0772] Rf 111 is a fluorine-containing monomer in which Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms;

[0773] Rf 111 is a group represented by the following formula:

[0774] [Chemical Formula 40]

[0775]

[0776] is a fluorine-containing monomer in which Rf is a group represented by the following formula:

[0777] Rf 111 is a group represented by the following formula:

[0778] [Chemical Formula 41]

[0779]

[0780] is a fluorine-containing monomer in which Rf is a group represented by the following formula: and the like.

[0781] As the fluorine-substituted alkyl vinyl ether, at least one selected from the group consisting of the fluorine-containing monomers represented by General Formulas (110), (130), and (140) is preferable.

[0782] As the fluorine-containing monomer represented by General Formula (110), at least one selected from the group consisting of a perfluoro(methyl vinyl ether), a perfluoro(ethyl vinyl ether), and a perfluoro(propyl vinyl ether) is preferable, and at least one selected from the group consisting of a perfluoro(methyl vinyl ether) and a perfluoro(propyl vinyl ether) is more preferable.

[0783] As the fluorine-containing monomer represented by General Formula (130), at least one selected from the group consisting of CF2=CFOCF2OCF3, CF2=CFOCF2OCF2CF3, and CF2=CFOCF2OCF2CF2OCF3 is preferable.

[0784] As the fluorine-containing monomer represented by General Formula (140), 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 is preferable.

[0785] As the fluorine-containing monomer represented by General Formula (150), at least one selected from the group consisting of CF2=CFOCF2CF2SO2F, CF2=CFOCF2CF(CF3)OCF2CF2SO2F, CF2=CFOCF2CF(CF2CF2SO2F)OCF2CF2SO2F, and CF2=CFOCF2CF(SO2F)2 is preferable.

[0786] As the fluorine-containing monomer represented by General Formula (100), Rf 101 As the fluorine-containing monomer in which the fluoroalkyl group is a linear fluoroalkyl group, Rf 101 As the fluorine-containing monomer in which the fluoroalkyl group is a linear perfluoroalkyl group, Rf 101 The number of carbon atoms of Rf is preferably 1 to 6. As the fluorine-containing monomer represented by General Formula (100), CH2=CFCF3, CH2=CFCF2CF3, CH2=CFCF2CF2CF3, CH2=CFCF2CF2CF2H, CH2=CFCF2CF2CF2CF3, and the like can be given, of which CH2=CFCF3 representing 2,3,3,3-tetrafluoropropene is preferable.

[0787] As the fluoroalkyl ethylene, Rf

[0788] General Formula (170): CH2=CH-(CF2) n -X 171

[0789] (in the formula, X 171 is H or F, and n is an integer of 3 to 10) is preferable, and at least one selected from the group consisting of CH2=CH-C4F9 and CH2=CH-C6F 13 is more preferable.

[0790] As the above-mentioned fluoro vinyl heterocyclic compound, a fluoro vinyl heterocyclic compound represented by General Formula (230) can be given:

[0791] [Formula 42]

[0792]

[0793] (in the formula, X 231 and X 232 independently F, Cl, methoxy or fluoromethoxy, Y 231 is a formula Y 232 or a formula Y 233 .

[0794] [Chemical Formula 43]

[0795]

[0796] (in the formula, Z 231 and Z 232 independently F or fluorinated alkyl group having 1 to 3 carbon atoms).

[0797] As the monomer providing a crosslinking site, at least one selected from the group consisting of the following monomers is preferred, the monomers being:

[0798] General Formula (180): CX 181 2=CX 182 -R f 181 CHR 181 X 183

[0799] (in the formula, X 181 and X 182 independently hydrogen atom, fluorine atom or CH3, R f 181 is fluorinated alkylene group, perfluorinated alkylene group, fluorinated (poly)oxyalkylene group or perfluorinated (poly)oxyalkylene group, R 181 is hydrogen atom or CH3, X 183 is iodine atom or bromine atom) represented fluorine-containing monomer;

[0800] General Formula (190): CX 191 2=CX 192 -R f 191 X 193

[0801] (in the formula, X 191 and X 192 independently hydrogen atom, fluorine atom or CH3, R f 191 is fluorinated alkylene group, perfluorinated alkylene group, fluorinated polyoxyalkylene group or perfluorinated polyoxyalkylene group, X 193 is iodine atom or bromine atom) represented fluorine-containing monomer;

[0802] General Formula (200): CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 201

[0803] (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 -CH2I) ; and

[0804] General Formula (210): CH2=CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X 211

[0805] (in the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, X 211 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I) ; and

[0806] General Formula (220): CR 221 R 222 =CR 223 -Z 221 -CR 224 =CR 225 R 226

[0807] (in the formula, R 221 , R 222 , R 223 , R 224 , R 225 , and R 226 are the same or different and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z 221 is a linear or branched alkylene group having 1 to 18 carbon atoms which can have an oxygen atom, a cycloalkylene group having 3 to 18 carbon atoms, an at least partially fluorinated alkylene or oxyalkylene group having 1 to 10 carbon atoms, or

[0808] -(Q) p -CF2O-(CF2CF2O) m (CF2O) n -CF2-(Q) p -

[0809] (in the formula, Q is an alkylene or oxyalkylene group. p is 0 or 1. m / n is 0.2 to 5) ; and

[0810] X 183 and X193 Preferably it is an iodine atom. f 181 and R f 191 A perfluoroalkylene group having 1 to 5 carbon atoms is preferred. 181 Preferably, it is a hydrogen atom. 201 Preferably, it is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom or -CH2I. 211 Preferred is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom or -CH2OH.

[0811] As the fluoromethylenedioxolane, the following general formula is preferred:

[0812] [Chemistry 44]

[0813]

[0814] (Where R 231 a compound represented by a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group, a fluoro(poly)oxyalkyl group, or a perfluoro(poly)oxyalkyl group,

[0815] More preferably, it is selected from the following formula:

[0816] [Chemistry 45]

[0817]

[0818] At least one of the group consisting of the compounds represented.

[0819] The monomer providing a crosslinking site is preferably at least one selected from the group consisting of 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(CF3)CF2OCF(CF3)CH2OH, CH2=CHCF2CF2I, CH2=CH(CF2)2CH=CH2, CH2=CH(CF2)6CH=CH2 and CF2=CFO(CF2)5CN, more preferably at least one selected from the group consisting of CF2=CFOCF2CF(CF3)OCF2CF2CN and CF2=CFOCF2CF2CH2I.

[0820] As the fluorinated acrylate monomer, preferably, the monomer has the general formula (240):

[0821] CH2=C(-X 241 )-C(=O)-OY 241 -Rf 241

[0822] (Where, X 241 is H, CH3, F or Cl; Y 241 is a single bond, an aliphatic group with more than 1 carbon atom; Rf 241 A substance represented by an aliphatic group having 1 to 8 carbon atoms or a fluorinated alkyl group having 1 to 8 carbon atoms).

[0823] Y 241 For example, it is a linear or branched aliphatic group (especially an alkylene group) having 1 to 20 carbon atoms, for example, it can be of the formula -(CH2) x -(wherein x is 1 to 10).

[0824] Rf 241 Preferably it is a perfluoroalkyl group. 241 The number of carbon atoms in Rf is preferably 4 to 8, more preferably 4 to 6. 241 , examples include -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF3)3, -(CF2)4CF3, -(CF2)2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, -C8F 17 wait.

[0825] Specific examples of the fluorine-containing acrylate monomer include the following, but are not limited to these.

[0826] CH2=C(-H)-C(=O)-O-(CH2)2-Rf 241

[0827] CH2=C(-CH3)-C(=O)-O-(CH2)2-Rf 241

[0828] CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf 241

[0829] (Where Rf 241 as above)

[0830] As the non-fluorine-containing monomer, a hydrocarbon-based monomer reactive with the above-mentioned fluorine-containing monomer, etc. can be given. As the hydrocarbon-based monomer, for example, an olefin-based such as ethylene, propylene, butylene, isobutylene, etc.; an alkyl vinyl ether-based such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, etc.; a vinyl ester-based such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pentanoate, vinyl neopentanoate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl p-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, vinyl undecylenate, vinyl glycolate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxypentanoate, vinyl hydroxyisobutyrate, vinyl hydroxycyclohexanecarboxylate, etc.; an alkyl allyl ether-based such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, cyclohexyl allyl ether, etc.; an alkyl allyl ester-based such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester, etc. can be given.

[0831] As the non-fluorine-containing monomer, a hydrocarbon-based monomer containing a functional group (excluding a monomer providing a crosslinking site) can also be given. As the hydrocarbon-based monomer containing a functional group, for example, a hydroxyalkyl vinyl ether-based such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, hydroxycyclohexyl vinyl ether, etc.; a non-fluorine-containing monomer having a carboxyl group such as itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride, perfluorobutenoic acid, etc.; a non-fluorine-containing monomer having a glycidyl group such as glycidyl vinyl ether, glycidyl allyl ether, etc.; a non-fluorine-containing monomer having an amino group such as an aminoalkyl vinyl ether, an aminoalkyl allyl ether, etc.; a non-fluorine-containing monomer having an amide group such as (meth)acrylamide, hydroxymethyl acrylamide, etc. can be given.

[0832] As the non-fluorine-containing monomer having an amide bond, for example, a monomer having the above-mentioned -CONR k 2, -NR x COR y , or a monomer having a lactam structure having 2 to 7 carbon atoms. The above-mentioned amide bond refers to a bond between a carbonyl group and a nitrogen atom.

[0833] As the non-fluorine monomer having an amide bond, there can be mentioned N-vinyl-β-propiolactam, N-vinyl-2-pyrrolidinone, N-vinyl-γ-valerolactam, N-vinyl-2-piperidinone, N-vinyl- caprolactam, and the like N-vinyl lactam compounds, N-vinyl formamide, N-methyl-N-vinyl acetamide, and the like acyclic N-vinyl amide compounds, N-allyl-N-methyl formamide, allyl urea, and the like acyclic N-allyl amide compounds, 1-(2-propenyl)-2-pyrrolidinone, and the like N-allyl lactam compounds, (meth)acrylamide, N,N-dimethyl acrylamide, N-isopropyl acrylamide, and the like acrylamide compounds.

[0834] As the non-fluorine monomer having an amide bond, there can be mentioned

[0835] [Chemical Formula 46]

[0836]

[0837] (In the formula, R x and R y independently represent H or an alkyl group having 1 to 10 carbon atoms, and the like.

[0838] [Chemical Formula 47]

[0839]

[0840] (In the formula, R z independently represent H or an alkyl group having 1 to 10 carbon atoms, and the like.

[0841] As the non-fluorine monomer having an amide bond, there can be mentioned N-vinyl-β-propiolactam, N-vinyl-2-pyrrolidinone, N-vinyl-γ-valerolactam, N-vinyl-2-piperidinone, N-vinyl- caprolactam, and the like N-vinyl lactam compounds, N-vinyl formamide, N-methyl-N-vinyl acetamide, and the like acyclic N-vinyl amide compounds, N-allyl-N-methyl formamide, allyl urea, and the like acyclic N-allyl amide compounds, 1-(2-propenyl)-2-pyrrolidinone, and the like N-allyl lactam compounds, (meth)acrylamide, N,N-dimethyl acrylamide, N-isopropyl acrylamide, and the like acrylamide compounds.

[0842] As the monomer other than TFE, there is preferably at least one selected from the group consisting of the following monomers:

[0843] the following general formula (1):

[0844] CF2=CR p R q

[0845] (In the formula, R p is H or F; and Rq -Cl, -CF3, -R a , -COOR b , -OCOR C , -CONR d 2, -CN, -COR e , -Rf a , -ORf b ; R a , R b , R c , R d and R e are the same or different and are H or a substituent; Rf a is a fluorine-containing alkyl group or a fluorine-containing vinyl group which can have a substituent and can contain an oxygen atom between carbon atoms; Rf b is a fluorine-containing alkyl group; R p and R q may be bonded to each other to form a ring) ; and

[0846] monomers represented by the following general formula (2) :

[0847] CH2=CR s R t

[0848] (in the formula, R s is R g , CF3or F; R t is -Cl, -R h , -COOR i , -OCOR j , -CONR k 2, -CN, -COR m , Rf c ; R g and R h are the same or different and are H or a hydrocarbon group or a heterocyclic group with or without a substituent; Rf i , R j , R k and R m are the same or different and are H or a substituent; Rf c is a fluorine-containing alkyl group, a fluorine-containing vinyl group or a fluorine-containing alkoxy group which can have a substituent and can contain an oxygen atom between carbon atoms; Rf s and R t may be bonded to each other to form a ring).

[0849] R a , R b , R c , R d and R eare the same or different and are H or a substituent. As the substituent, the above groups can be cited, among which aliphatic groups, acyl groups, aromatic groups or heterocyclic groups are preferred, aliphatic groups, acyl groups or heterocyclic groups are more preferred, and aliphatic groups or acyl groups are further preferred. a 、R b 、R c 、R d and R e The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5. The above-mentioned aliphatic group, acyl group, aromatic group and heterocyclic group may have a substituent, may have an oxygen atom between carbon atoms, and some or all of the hydrogen atoms bonded to carbon atoms may be substituted with fluorine (for example, a fluorinated alkyl group, particularly a perfluoroalkyl group).

[0850] R a 、R b 、R c 、R d and R e It may be chain-like or branched, and may include a ring structure.

[0851] It should be noted that R in the general formula (1) a It can be a substituent other than -CF3, such as R a In the case of a perfluoroalkyl group, R a The number of carbon atoms may be 2 or more.

[0852] As Rf in the general formula (1) a , fluorinated alkyl groups, fluorinated vinyl groups, fluorinated alkoxy groups, fluorinated alkyloxyalkyl groups, etc., which may have a substituent and may contain an oxygen atom between carbon atoms, are mentioned. a The number of carbon atoms in alkyl is preferably 1-10, more preferably 1-8, and even more preferably 1-6.

[0853] Rf a It may be chain-like or branched, and may include a ring structure.

[0854] Rf in the general formula (1) b is a fluorinated alkyl group. b The number of carbon atoms in Rf is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and still further preferably 1 to 3. b It may be in the form of a chain or a branched chain, and may include a ring structure, but is preferably in the form of a chain.

[0855] As the above R q, preferably -H, a fluorine-containing alkyl group having or not having a substituent and having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having or not having a substituent and having 1 to 10 carbon atoms, -Cl, a non-fluorine-containing alkyl group having or not having a substituent and having 1 to 10 carbon atoms, a carboxyl group, an alkyl ester group having or not having a substituent and having 1 to 10 carbon atoms, or a fluorine-containing alkyloxyalkyl group having or not having a substituent and having 1 to 10 carbon atoms, preferably -H, -CF3, -OCF3, -OCF2CF2SO2F, -Cl, -CH3, -OCH2CF3, -COOH, -COOCH3, -OCF2OCF3, -OCF2CF2OCF3, -OCF2CF2CF2OCF3, or -OC3F7, more preferably -H, -CF3, -OCF3, -OC3F7, or -OCF2CF2SO2F, further preferably -H, -CF3, or -OCF3.

[0856] As the monomer represented by the above general formula (1), at least one selected from the group consisting of HFP, CTFE, VDF, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, and hexafluoroisobutylene is preferable.

[0857] As the fluoroalkyl vinyl ether, the above-mentioned substance can be mentioned.

[0858] As the monomer represented by the above general formula (1), a monomer represented by general formula (200), a monomer represented by general formula (210) can also be mentioned. In general formula (200) and general formula (210), n is preferably an integer of 5 or less. 1 -CF3is preferable.

[0859] R 7 H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, further preferably H or a C 1-4 alkyl group.

[0860] As the metal atom, an alkali metal (Group 1), an alkaline earth metal (Group 2), or the like can be mentioned, and Na, K, or Li is preferable.

[0861] M is preferably -H, a metal atom, or -NR 7 4, more preferably -H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or -NR 7 4, further preferably -H, -Na, -K, -Li, or -NH4.

[0862] As the monomer represented by the above general formula (1), the following general formula (270) can also be mentioned:

[0863] [Chemical Formula 48]

[0864]

[0865] (in the formula, Rf 1 , Rf 2 , Rf 3 , and Rf 4 are the same or different and represent F or a perfluoroalkyl group having 1 to 10 carbon atoms), and a monomer represented by the following general formula (280) :

[0866] [Chemical Formula 49]

[0867]

[0868] (in the formula, Rf 5 , and Rf 6 represent F or a perfluoroalkyl group having 1 to 10 carbon atoms).

[0869] As the monomer represented by the general formula (1), VDF, HFP, perfluoro (methyl vinyl ether), perfluoro fluorosulfonyl vinyl ether, trifluoroethylene, CTFE, or trifluoropropylene is preferred, VDF, HFP, perfluoro (methyl vinyl ether), perfluoro fluorosulfonyl vinyl ether, or trifluoropropylene is more preferred, and VDF, HFP, or perfluoro (methyl vinyl ether) is further preferred.

[0870] The monomer represented by the general formula (1) is a monomer different from TFE.

[0871] R g , and R h in the general formula (2) are the same or different and represent H or a hydrocarbon group with or without a substituent or a heterocyclic group. As the hydrocarbon group, an alkyl group, an alkylene group, an aryl group, a vinyl group, or the like can be given. The number of carbon atoms of the hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10.

[0872] As the heterocyclic group, a group having a lactam structure having 2 to 7 carbon atoms is preferred, a group having a lactam structure having 3 to 6 carbon atoms is more preferred, and a group having a lactam structure having 4 carbon atoms is further preferred.

[0873] R g , and R h may be linear or branched, and can include a cyclic structure.

[0874] R i , R j , R k , and R mThe same or different, H or a substituent. As the above substituent, there can be mentioned the above groups, of which aliphatic group, acyl group, aromatic group or heterocyclic group is preferred, aliphatic group, acyl group or heterocyclic group is more preferred, and aliphatic group or acyl group is further preferred. The above aliphatic group, acyl group, aromatic group and heterocyclic group can have a substituent, and can have an oxygen atom between carbon atoms. The above R i , R j , R k and R m preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and further preferably 1 to 10 carbon atoms.

[0875] R i , R j , R k and R m may be linear or branched, and can have a cyclic structure.

[0876] As Rf c in General Formula (2), there can be mentioned fluorine-containing alkyl group, fluorine-containing vinyl group, fluorine-containing alkoxy group, fluorine-containing alkyloxyalkyl group and the like, which can have a substituent and can have an oxygen atom between carbon atoms. Rf c preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 6 carbon atoms.

[0877] Rf c may be linear or branched, and can have a cyclic structure.

[0878] As the above R s , H, F, CH3or CF3is preferred, and H, F or CF3is more preferred.

[0879] As the above R t , non-fluorine-containing alkyl group having 1 to 10 carbon atoms with or without a substituent, fluorine-containing alkyl group having 1 to 10 carbon atoms with or without a substituent, -COOR i , -OCOR j , -CONR k 2, -NR x COR y , -NR z 2or a group having a lactam structure having 2 to 7 carbon atoms are preferred.

[0880] The above R x , R y and R z are the same or different, and are H or alkyl group having 1 to 10 carbon atoms.

[0881] Examples of the monomer represented by the general formula (2) include olefins such as ethylene, propylene, butene, and isobutylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl octanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl adipate, vinyl acrylate, and vinyl methacrylate. , vinyl crotonate, vinyl sorbate, vinyl cinnamate, vinyl undecylenate, vinyl hydroxyacetate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, vinyl hydroxycyclohexanecarboxylate and other vinyl esters; alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, cyclohexyl allyl ether; alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester, etc.

[0882] Examples of the monomer represented by the general formula (2) include (meth)acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; itaconic acid; non-fluorinated monomers having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether; non-fluorinated monomers having an amino group such as aminoalkyl vinyl ether and aminoalkyl allyl ether; and non-fluorinated monomers having an amide bond such as (meth)acrylamide and hydroxymethyl acrylamide.

[0883] Examples of the monomer represented by the general formula (2) include fluoroethylene, fluoroalkylethylene, fluorinated monomers represented by the general formula (100), and the general formula (300): CH2=CFCF2-O-(CF(CF3)CF2O) n -CF(CF3)-A (wherein n represents an integer of 0 or 1 to 10, A represents -CH2OH, -COOM, -SO3M or -OSO3M (M represents -H, metal atom, -NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group)) a fluorinated monomer, a fluorinated acrylate monomer, and the like.

[0884] In the above general formula (300), n is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1. 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4alkyl. As the metal atom, an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be given, and Na, K or Li is preferred. As M, -H, a metal atom or -NR 7 4, more preferably -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7 4, further preferably -H, -Na, -K, -Li or -NH4.

[0885] As R t , preferably -OCOCH3, -H, -COOCH3, -NH(C3H7), -C4F9, -CH3, or the following formula (3):

[0886] [Chemical Formula 50]

[0887]

[0888] the group represented by the above formula (3), further preferably -OCOCH3, -H or the group represented by the above formula (3).

[0889] As the monomer represented by General Formula (2), a vinyl ester, a (meth)acrylate, an olefin, a non-fluorine-containing monomer having an amide bond, a fluoroalkyl vinyl or a fluorine-containing acrylate monomer is preferred, a vinyl ester, a (meth)acrylate, an olefin, an N-acrylamide compound, an N-vinylamide compound, an N-vinyl lactam compound, a fluoroalkyl vinyl or a fluorine-containing acrylate monomer is more preferred, and vinyl acetate, N-vinylpyrrolidone, ethylene, methyl acrylate, N-isopropyl acrylamide or CH2=CH-C4F9is particularly preferred.

[0890] As the monomer other than TFE, it is particularly preferable that at least one selected from the group consisting of HFP, CTFE, VDF, fluoroethylene, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropene, pentafluoropropene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl esters, (meth)acrylate, olefin, non-fluorine-containing monomer having an amide bond, fluoroalkyl ethylene, and fluorine-containing acrylate monomer, more preferable that at least one selected from the group consisting of HFP, CTFE, VDF, fluoroethylene, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropene, pentafluoropropene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl esters, (meth)acrylate, acrylamide, vinylamide, fluoroalkyl ethylene, and fluorine-containing acrylate monomer, further preferable that at least one selected from the group consisting of HFP, CTFE, VDF, fluoroalkyl vinyl ether, trifluoropropene, pentafluoropropene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl esters, (meth)acrylate, N-acrylamide compound, vinylamide compound, N-vinyl lactam compound, fluoroalkyl ethylene, and fluorine-containing acrylate monomer, further more preferable that at least one selected from the group consisting of HFP, VDF, perfluoro(methyl vinyl ether), perfluoro fluorosulfonyl vinyl ether, ethylene, N-vinylamide compound, N-vinyl lactam compound, and vinyl acetate, particularly preferable that at least one selected from the group consisting of HFP, VDF, perfluoro(methyl vinyl ether), perfluoro fluorosulfonyl vinyl ether, ethylene, N-vinylamide compound, N-vinyl pyrrolidone, and vinyl acetate.

[0891] As the monomer other than TFE in the production method of the present application, a compound having a functional group capable of reacting in radical polymerization and a hydrophilic group can also be mentioned. For example, the following compounds can be mentioned:

[0892] General Formula (270a):

[0893] CF2=CF-(CF2) n271a -Y 271

[0894] (In the formula, n271a represents an integer of 1 to 10, Y 271 represents -SO3M 271 or -COOM 271 , M 271 represents H, NH4, or an alkali metal); and General Formula (270b):

[0895] CF2=CF-(CF2C(CF3)F) n271b -Y 271

[0896] (In the formula, n271b represents an integer of 1 to 5, Y271 a compound represented by General Formula (270c) :

[0897] CF2=CF-O-(CFX 271 ) n271c -Y 271

[0898] (In the formula, X 271 represents F or CF3, n271c represents an integer of 1 to 10, and Y 271 a compound represented by General Formula (270d) :

[0899] CF2=CF-O-(CF2CFX 271 O) n271d -CF2CF2-Y 271

[0900] (In the formula, n271d represents an integer of 1 to 10, and Y 271 and X 271 a compound represented by General Formula (270e) :

[0901] CX 272 2=CFCF2-O-(CF(CF3)CF2O) n271e -CF(CF3)-Y 271

[0902] (In the formula, each X 272 is the same and represents F or H. n271e represents 0 or an integer of 1 to 10, and Y 271 a compound represented by General Formula (270f) or the like.

[0903] The above polymerization procedure can produce modified PTFE containing 99.0 mass% or more of TFE units and 1.0 mass% or less of polymerization units based on monomers other than TFE, and the above polymerization procedure is preferably polymerization in a manner such that the total amount of polymerization units based on monomers other than TFE is 0.00001 to 1.0 mass%. As a lower limit of the above total amount, 0.0001 mass% is more preferable, 0.001 mass% is further preferable, 0.005 mass% is further more preferable, and 0.009 mass% is particularly preferable. As an upper limit, 0.90 mass% is preferable, 0.50 mass% is more preferable, 0.40 mass% is further preferable, 0.30 mass% is further more preferable, and 0.10 mass% is especially further preferable.

[0904] In this case, the monomer other than TFE described above can be a monomer represented by General Formula (1) or General Formula (2), and is more preferably at least one selected from the group consisting of HFP, VDF, perfluoro(methyl vinyl ether), perfluoro fluoro sulfonyl vinyl ether, ethylene, an N-vinyl amide compound, N-vinyl pyrrolidone, and vinyl acetate.

[0905] The production method of the present application can include a step of forming an oleophilic nucleation site in the aqueous medium described above (hereinafter also referred to as "nucleation site forming step").

[0906] By performing the polymerization in the presence of the oleophilic nucleation site described above, even if the addition of the surfactant described above is performed after the start of the polymerization reaction, the polymerization can be effectively performed. In addition, compared to the case where the polymerization is performed in the absence of the oleophilic nucleation site described above, a fluoropolymer having a small primary particle diameter can be obtained.

[0907] The nucleation site forming step described above can be a step of providing an aqueous dispersion of the oleophilic nucleation site described above.

[0908] The nucleation site forming step described above is preferably performed before the start of the polymerization reaction in the polymerization step described above.

[0909] The oleophilic nucleation site described above preferably does not contain a polymerized monomer.

[0910] The oleophilic nucleation site described above is dispersed in the aqueous medium, and the growth of the fluoropolymer particles can be performed at this site. By forming the fluoropolymer particles at the oleophilic nucleation site described above, an initial dispersion of the fluoropolymer particles described above can be provided.

[0911] The oleophilic nucleation site described above can be formed, for example, by decomposing a nucleating agent, and is preferably formed by adding a nucleating agent and a decomposing agent in the aqueous medium.

[0912] As the nucleating agent described above, a water-soluble hydrocarbon-containing compound containing a hydrophobic portion and a hydrophilic portion can be given, and examples thereof include a dicarboxylic acid, a perfluoro polyether (PFPE) acid or a salt thereof, a hydrocarbon-containing surfactant, and the like. The nucleating agent described above preferably does not contain an aromatic ring, and is preferably an aliphatic compound.

[0913] The hydrocarbon-containing surfactant described above as the nucleating agent described above is preferably different from the surfactant in the polymerization step, and is preferably a nonionic surfactant.

[0914] As the preferable amount of the above-mentioned nucleating agent, 1000 ppm or less, relative to the above-mentioned aqueous medium, can be appropriately selected depending on the kind of the nucleating agent, 500 ppm or less can be more preferable, 100 ppm or less can be further preferable, 50 ppm or less can be particularly preferable, and 10 ppm or less can be especially further preferable.

[0915] As the preferable amount of the above-mentioned dicarboxylic acid, 1000 ppm or less, relative to the above-mentioned aqueous medium, can be appropriately selected depending on the kind of the dicarboxylic acid, 500 ppm or less can be more preferable, and 100 ppm or less can be further preferable.

[0916] The above-mentioned perfluoropolyether (PFPE) acid or salt thereof can have any chain structure in which the oxygen atom in the molecular main chain is separated by a saturated fluorocarbon group having 1 to 3 carbon atoms. In addition, two or more kinds of fluorocarbon groups can be present in the molecule. A representative structure has a repeating unit represented by the following formula:

[0917] (-CFCF3-CF2-O-) n (VII)

[0918] (-CF2-CF2-CF2-O-) n (VIII)

[0919] (-CF2-CF2-O-) n -(-CF2-O-) m (IX)

[0920] (-CF2-CFCF3-O-) n -(-CF2-O-) m (X)

[0921] These structures are described by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed in this document, the above-mentioned PFPE acid or salt thereof can have a carboxylic acid group or salt thereof at one or both of the terminals. The above-mentioned PFPE acid or salt thereof can also have a sulfonic acid, phosphonic acid group or salt thereof at one or both of the terminals. In addition, the above-mentioned PFPE acid or salt thereof can have different groups at each terminal. With respect to the monofunctional PFPE, the other terminal of the molecule is typically perfluorinated, but can also contain hydrogen or chlorine atoms. The above-mentioned PFPE acid or salt thereof has at least 2 ether oxygens, preferably at least 4 ether oxygens, further more preferably at least 6 ether oxygens. Preferably, at least one, more preferably at least two of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. Further more preferably, at least 50% of the fluorocarbon groups separating the ether oxygens have 2 or 3 carbon atoms. In addition, it is preferred that the above-mentioned 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 above-mentioned repeating unit structure is at least 5. Two or more of the above-mentioned PFPE acids or salts thereof having an acid group at one or both of the terminals can be used in the production method of the present application. The above-mentioned PFPE acid or salt thereof preferably has a number average molecular weight of less than 6000 g / mole.

[0922] The above-mentioned hydrocarbon-containing surfactant is preferably added in an amount of 40 ppm or less, more preferably 30 ppm or less, further more preferably 20 ppm or less, with respect to the above-mentioned aqueous medium. It is presumed that the amount of the oleophilic nucleation sites present in the above-mentioned aqueous medium is less than the above-mentioned added amount. Therefore, the amount of the above-mentioned oleophilic nucleation sites is less than the above-mentioned 50 ppm, 40 ppm, 30 ppm, 20 ppm, respectively. The above-mentioned oleophilic nucleation sites are considered to exist in the form of molecules, and therefore a large amount of the oleophilic nucleation sites can be generated even with an extremely small amount of the above-mentioned hydrocarbon-containing surfactant. Therefore, even if the above-mentioned hydrocarbon-containing surfactant is added to the aqueous medium in an amount of about 1 ppm or less, a beneficial effect can be obtained. It is preferred that the lower limit value is 0.01 ppm, more preferably 0.1 ppm.

[0923] The above-mentioned hydrocarbon-containing surfactant includes a silicone surfactant such as those disclosed in U.S. Patent No. 7,897,682 (Brothers et al.) and U.S. Patent No. 7,977,438 (Brothers et al.), and includes nonionic surfactants and cationic surfactants.

[0924] As the above-mentioned hydrocarbon-containing surfactant, a nonionic hydrocarbon surfactant is preferred. That is, as the nucleation surfactant, a nonionic hydrocarbon surfactant is preferred. The above-mentioned nonionic hydrocarbon surfactant preferably does not contain an aromatic moiety.

[0925] As the above-mentioned nonionic hydrocarbon surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, glycerin ester, derivatives thereof, and the like can be given. More specifically, examples of the polyoxyethylene alkyl ether are polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like; examples of the polyoxyethylene alkyl phenyl ether are polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, and the like; examples of the polyoxyethylene alkyl ester are polyethylene glycol monolaurylate, polyethylene glycol monooleate, polyethylene glycol monostearate, and the like; examples of the sorbitan alkyl ester are polyoxyethylene sorbitan monolaurylate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like; examples of the polyoxyethylene sorbitan alkyl ester are polyoxyethylene sorbitan monolaurylate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and the like; examples of the glycerin ester are glyceryl monomyristate, glyceryl monostearate, glyceryl monooleate, and the like. In addition, examples of the derivatives thereof are polyoxyethylene alkyl amine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, and the like. The polyoxyethylene alkyl ether and the polyoxyethylene alkyl ester are particularly preferable. Examples of such ethers and esters are substances having an HLB value of 10 to 18. More specifically, there are polyoxyethylene lauryl ether (EO: 5 to 20. EO represents an ethylene oxide unit), polyethylene glycol monostearate (EO: 10 to 55), and polyethylene glycol monooleate (EO: 6 to 10).

[0926] As a suitable nonionic hydrocarbon surfactant, octylphenol ethoxylate such as Triton (registered trademark) X series supplied by Dow Chemical Company can be given:

[0927] [Chemical Formula 51]

[0928]

[0929] Triton (registered trademark)

[0930] X15: n = 1.5 (avg)

[0931] X45: n = 4.5 (avg)

[0932] Preferred nonionic hydrocarbon surfactants are branched alcohol ethoxylates such as the Tergitol (Registered Trademark) 15-S series supplied by the Dow Chemical Company, and branched secondary alcohol ethoxylates such as the Tergitol (Registered Trademark) TMN series supplied by the Dow Chemical Company:

[0933] [Chem. 52]

[0934]

[0935] Tergitol (Registered Trademark)

[0936] TMN-6: n = 8 (avg)

[0937] TMN-10: n = 11 (avg)

[0938] TMN-100: n = 10 (avg)

[0939] Tergitol (Registered Trademark) L series surfactants supplied by the Dow Chemical Company, such as ethylene oxide / propylene oxide copolymers, are also useful as the nonionic hydrocarbon surfactant described above.

[0940] Further, another useful group of suitable nonionic hydrocarbon surfactants are difunctional block copolymers such as those supplied by BASF as Pluronic (Registered Trademark) R series:

[0941] [Chem. 53]

[0942]

[0943] Pluronic (Registered Trademark)

[0944] 31R1: m = 26 (avg), n = 8 (avg)

[0945] 17R2: m = 14 (avg), n = 9 (avg)

[0946] 10R5: m = 8 (avg), n = 22 (avg)

[0947] 25R4: m = 22 (avg), n = 23 (avg)

[0948] Another group of suitable nonionic hydrocarbon surfactants are tridecyl alcohol alkoxylates supplied by BASF Corporation as Iconol (Registered Trademark) TDA series.

[0949] [Chem. 54]

[0950]

[0951] Iconol (registered trademark)

[0952] TDA-6: n = 6 (avg)

[0953] TDA-9: n = 9 (avg)

[0954] TDA-10: n = 19 (avg)

[0955] The above-mentioned cationic surfactant can also be used as a nucleating surfactant. A representative cationic surfactant has a positively charged hydrophilic moiety such as an alkylated ammonium halide (alkylated ammonium bromide, etc.) and a hydrophobic moiety such as a long-chain fatty acid.

[0956] Another group of nucleating agents that can be used are hydrocarbon-containing siloxane surfactants, preferably hydrocarbon surfactants, where the above-mentioned hydrocarbon groups can be replaced by halogens such as fluorine, provided that they are completely replaced by hydrogen atoms, whereby these siloxane surfactants can also be regarded as hydrocarbon surfactants, i.e. the monovalent substituents on the hydrocarbon groups are hydrogen. As nucleating agents, hydrocarbon siloxanes having nonionic moieties, i.e. nonionic hydrocarbon (siloxane) surfactants, are preferred.

[0957] The above-mentioned decomposition agent used in the decomposition of the above-mentioned nucleating agent is preferably an oxidizing agent, more preferably a free radical polymerization initiator that can also be used in the polymerization of the fluoromonomer.

[0958] As the above-mentioned polymerization initiator, for example, a high-activity water-soluble salt of an inorganic initiator such as an inorganic peracid can be mentioned, of which a persulfate salt such as ammonium persulfate or potassium persulfate is preferred. The above-mentioned persulfate salt preferably substantially contains no metal ions, more preferably is an ammonium salt.

[0959] As the above-mentioned polymerization initiator, a water-soluble organic azo compound such as an azo amidine compound is also useful.

[0960] The above-mentioned polymerization initiator and the polymerization initiator used in the polymerization of the fluoromonomer can be the same or different.

[0961] The amount of the above-mentioned decomposition agent added to the aqueous medium is preferably less than the amount required to initiate the polymerization reaction, and is preferably 50 ppm or less, more preferably 40 ppm or less, still more preferably 30 ppm or less, yet more preferably 20 ppm or less, most preferably 15 ppm or less, relative to the above-mentioned aqueous medium. The lower limit of the amount of the above-mentioned decomposition agent is, for example, 1 ppm.

[0962] The decomposition of the above nucleating agent is preferably performed in the presence of an inorganic salt. This makes it possible to increase the number of the above lipophilic nucleation sites formed, and to obtain a fluoropolymer having a smaller primary particle diameter.

[0963] As examples of the above inorganic salt, water-soluble inorganic salts can be given, and for example, salts containing alkali metal cations such as Na, K, etc., NH4 + cations such as -SO3, -HSO3, -NO3 - , -Cl - , -CO3 - , -B4O7 - , -HPO4 - , etc. can be given. In the case where the fluoropolymer produced by polymerization is processed by melt extrusion, the salt is preferably an ammonium salt.

[0964] The amount of the above inorganic salt present in the aqueous medium at the time of the decomposition (oxidation) reaction of the above nucleating agent with respect to the above aqueous medium is preferably 100 ppm or less, more preferably 75 ppm or less, further preferably 50 ppm or less, and most preferably 25 ppm or less. In the case of use, the lower limit of the amount can be 1 ppm.

[0965] In addition, in the production method of the present application, an additive for stabilizing each compound can be used in addition to the above surfactant and other compounds having surface activity ability as desired. As the above additive, a buffer, a pH adjustor, a stabilizing aid, a dispersion stabilizer, etc. can be given.

[0966] As the stabilizing aid, paraffin, fluorine-based oil, fluorine-based solvent, silicone oil, etc. are preferred. The stabilizing aid can be used alone or in combination of two or more. As the stabilizing aid, paraffin is more preferred. As paraffin, it can be liquid, can be semi-solid, or can be solid at room temperature, and a saturated hydrocarbon having 12 or more carbon atoms is preferred. The melting point of paraffin is generally preferably 40 to 65°C, and more preferably 50 to 65°C.

[0967] The amount of the stabilizing aid is preferably 0.1 to 12 mass%, and more preferably 0.1 to 8 mass%, based on the mass of the aqueous medium used. The stabilizing aid is preferably sufficiently hydrophobic, and is completely separated from the PTFE aqueous emulsion after emulsion polymerization of TFE, and does not become a contaminating component.

[0968] In the production method of the present application, the necessary additives such as an aqueous medium, TFE, a chain transfer agent, and an initiator are charged into a polymerization reactor, the contents of the reactor are stirred, and the reactor is maintained at a prescribed polymerization temperature, and then a specific amount of an initiator is added to initiate the polymerization reaction, whereby the above-mentioned polymerization step is performed. The monomer, the initiator, the chain transfer agent, and the like can be added additionally after the start of the polymerization reaction as necessary. The timing of addition of the above-mentioned surfactant can be determined as necessary, and the above-mentioned surfactant can be added at any timing before, at, or after the start of the polymerization reaction, or can be added at two or more of them.

[0969] In the above-mentioned polymerization, the polymerization temperature is usually 5 to 120°C, preferably 10 to 100°C, and more preferably 20 to 90°C. The polymerization pressure is usually 0.05 to 10 MPaG, preferably 0.1 to 5.0 MPaG, and more preferably 0.2 to 3.0 MPaG. The polymerization temperature and the polymerization pressure are suitably determined in accordance with the kind of the monomer used, the molecular weight of the target fluorine-containing polymer, and the reaction rate.

[0970] The above-mentioned surfactant is preferably added in an amount of 0.0001 to 10% by mass based on 100% by mass of the aqueous medium. The more preferable lower limit is 0.001% by mass, and the more preferable upper limit is 1% by mass. If less than 0.0001% by mass, the dispersing force can be insufficient, and if more than 10% by mass, an effect commensurate with the amount added can not be obtained, and instead, a decrease in the polymerization rate or a reaction stoppage can occur. The amount of the above-mentioned surfactant added is suitably determined in accordance with the kind of the monomer used, the molecular weight of the target fluorine-containing polymer, and the like.

[0971] The above-mentioned aqueous medium refers to a reaction medium in which the above-mentioned polymerization of TFE is performed, and is a liquid containing water. The above-mentioned aqueous medium is not particularly limited as long as it contains water, and can contain water, and a non-fluorine-containing organic solvent such as an alcohol, an ether, a ketone, and the like, and / or a fluorine-containing organic solvent having a boiling point of 40°C or lower.

[0972] As the fluorine-containing polymer produced by the production method of the present application, a TFE homopolymer can be used, or a copolymer composed of greater than 80% by mole of TFE units and less than 20% by mole of polymerization units based on the above-mentioned monomer other than TFE can be used.

[0973] As the fluorine-containing polymer produced by the production method of the present application, the fluorine-containing polymer of the present application described later can be used.

[0974] The fluorine-containing polymer of the present application is represented by the following formula:

[0975] Af-CRP

[0976] (In the formula, Af is a fluoropolymer segment containing more than 80 mol% of polymerized units based on TFE. CRP is any one of the following formulas (CRP1) to (CRP5)).

[0977] Formula (CRP1):

[0978] -SC(S)Z c11

[0979] (In the formula, Z c11 is an alkyl group or an aryl group.)

[0980] Formula (CRP2):

[0981] -SC(S)SZ c12

[0982] (In the formula, Z c12 is an alkyl group or an aryl group.)

[0983] Formula (CRP3):

[0984] -SC(S)SR c11

[0985] (In the formula, R c11 is a monovalent organic group.)

[0986] Formula (CRP4):

[0987] -SC(S)NZ c13 2

[0988] (In the formula, Z c13 (i) is independently an alkyl group, an aryl group or a 4-pyridyl group, or (ii) is a group that is bonded to each other and forms a heterocycle together with the N atom in the formula.)

[0989] Formula (CRP5):

[0990] -SC(S)OZ c14

[0991] (In the formula, Z c14 is an alkyl group or an aryl group.)

[0992] In the past, it has been difficult to perform block copolymerization in TFE-based polymers. In the fluoropolymer of the present application, block copolymerization can be performed by having the above specific group at the terminal. Therefore, the fluoropolymer of the present application is also useful as an intermediate for producing a block copolymer.

[0993] In addition, the fluoropolymer of the present application can be used not only as an intermediate but also directly in the above uses.

[0994] As Z c11The same group as Z in the above-mentioned formula (c1-1) can be exemplified. c1 The same group as Z in the above-mentioned formula (c1-1) can be exemplified.

[0995] The same group as Z in the above-mentioned formula (c1-1) can be exemplified. c12 The same group as Z in the above-mentioned formula (c1-2) can be exemplified. c2 The same group as Z in the above-mentioned formula (c1-2) can be exemplified.

[0996] The same group as R in the above-mentioned formula (c1-2') can be exemplified. c11 The same group as R in the above-mentioned formula (c1-2') can be exemplified. r The same group as R in the above-mentioned formula (c1-2') can be exemplified.

[0997] The same group as Z in the above-mentioned formula (c1-3) can be exemplified. c13 The same group as Z in the above-mentioned formula (c1-3) can be exemplified. c3 The same group as Z in the above-mentioned formula (c1-3) can be exemplified. c4 The same group as Z in the above-mentioned formula (c1-3) can be exemplified.

[0998] The same group as Z in the above-mentioned formula (c1-4) can be exemplified. c14 The same group as Z in the above-mentioned formula (c1-4) can be exemplified. c5 The same group as Z in the above-mentioned formula (c1-4) can be exemplified.

[0999] Among the above-mentioned CRPs, (CRP5) is preferable from the viewpoint of polymerization rate.

[1000] The above-mentioned formulae (CRP1) to (CRP5) are groups of chain transfer agents described in the production method of the present application. In other words, the above-mentioned formulae (CRP1) to (CRP5) are moieties in which at least a part of the structure of the above-mentioned chain transfer agent is introduced into the fluorine-containing polymer (preferably, the terminal of the main chain of the fluorine-containing polymer).

[1001] The fluorine-containing polymer of the present application contains more than 80 mol% of TFE units. The TFE units are preferably 90 mol% or more, more preferably more than 90 mol%, further preferably 95 mol% or more, further more preferably 99 mol% or more.

[1002] The fluorine-containing polymer of the present application can also be a modified PTFE in which the polymerization units based on TFE are 99.0 mass% or more and the polymerization units based on monomers other than TFE are 1.0 mass% or less.

[1003] The above-mentioned Af is one suitable way in which the fluorine-containing polymer segment consisting only of monomer units from TFE.

[1004] In other words, the fluorine-containing polymer of the present application is preferably represented by the following formula:

[1005] Bf-CRP

[1006] (In the formula, Bf is a fluorine-containing polymer segment consisting only of polymerization units based on TFE. CRP is the same as described above).

[1007] The fluorine-containing polymer of which the above-mentioned Af is a fluorine-containing polymer chain segment composed of only monomer units from TFE is a so-called PTFE. The PTFE will be described below.

[1008] The PTFE obtained by the production method of the present application can be a low molecular weight PTFE or a high molecular weight PTFE.

[1009] The low molecular weight PTFE (also referred to as PTFE fine powder) having a molecular weight of 600,000 or less is excellent in chemical stability, has extremely low surface energy, and is not easily fibrillated, and thus is suitable for use as an additive for the purpose of improving smoothness, coating film surface texture, and the like in the production of plastics, inks, cosmetics, paints, greases, office automation equipment members, toners, and the like (for example, refer to Japanese Patent Laid-Open No. 10-147617).

[1010] In the case where the low molecular weight PTFE obtained by the above-mentioned polymerization is used as a powder, the powder particles can be produced by allowing the dispersion liquid of the PTFE to be sedimented.

[1011] The high molecular weight PTFE refers to a PTFE having non-melt processability and fibrillatability. On the other hand, the low molecular weight PTFE refers to a PTFE having melt processability and not having fibrillatability.

[1012] The above-mentioned non-melt processability refers to a property 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.

[1013] The presence or absence of fibrillatability can be judged by "paste extrusion", which is a representative method of molding a powder made of a polymer of TFE, i.e., "high molecular weight PTFE powder". This is because, generally, the high molecular weight PTFE has fibrillatability when paste extrusion can be performed. In the case where the un-fired molded article obtained by the paste extrusion does not have substantial strength and elongation, for example, the case where the elongation is 0% and breaks if stretched, it can be considered that the PTFE does not have fibrillatability.

[1014] The above-mentioned high molecular weight PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.280. The above-mentioned standard specific gravity is measured by a water displacement method according to ASTM D-792 using a sample molded according to ASTM D4895-89. "High molecular weight" refers to the above-mentioned standard specific gravity being within the above-mentioned range.

[1015] The above-mentioned low molecular weight PTFE has a complex viscosity at 380°C of 1 x 10 2 ~ 7 x 10 5Pa-s. "Low molecular weight" means that the complex viscosity is within the above range.

[1016] The complex viscosity of the high molecular weight PTFE is extremely high compared to the low molecular weight PTFE, and it is difficult to measure the accurate complex viscosity. On the other hand, the complex viscosity of the low molecular weight PTFE can be measured, but it is difficult to obtain a molded product that can be used in the measurement of the standard specific gravity from the low molecular weight PTFE, and it is difficult to measure the accurate standard specific gravity. Therefore, the standard specific gravity is used as an index of the molecular weight of the high molecular weight PTFE, and the complex viscosity is used as an index of the molecular weight of the low molecular weight PTFE. Note that the measurement method for directly determining the molecular weight is unknown for both the high molecular weight PTFE and the low molecular weight PTFE.

[1017] The peak temperature of the high molecular weight PTFE is preferably 333 to 347°C, and more preferably 335 to 345°C. The peak temperature of the low molecular weight PTFE is preferably 322 to 333°C, and more preferably 324 to 332°C. The peak temperature is the temperature corresponding to the maximum value in the heat of fusion curve when a differential scanning calorimeter [DSC] is used for the PTFE that has not experienced a heating history of heating to a temperature of 300°C or more, and the temperature is increased at a rate of 10°C / minute.

[1018] With respect to the high molecular weight PTFE, in the heat of fusion curve when a differential scanning calorimeter [DSC] is used for the PTFE that has not experienced a heating history of heating to a temperature of 300°C or more, and the temperature is increased at a rate of 10°C / minute, it is preferable that at least one or more endothermic peaks appear in the range of 333 to 347°C, and the heat of fusion calculated from the heat of fusion curve is 62 mJ / mg or more in the range of 290 to 350°C.

[1019] The PTFE can be used as an aqueous dispersion or a fine powder.

[1020] The fine powder of the PTFE is preferably used for molding, and as suitable uses, pipes for oil pressure systems, fuel systems, etc. of aircraft and automobiles, flexible hoses for liquid, vapor, etc., wire coating uses, etc. can be cited.

[1021] In addition, the aqueous dispersion of the PTFE is also preferably stabilized by adding a nonionic surfactant and further concentrated, and used for various uses in the form of a composition in which an organic or inorganic filler is added according to the purpose. The composition can be made into a coating film surface having non-adhesion and low friction coefficient, gloss, smoothness, excellent wear resistance, weather resistance, and heat resistance by being coated on a substrate composed of metal or ceramic, and is suitable for painting of rollers or cooking utensils, impregnation processing of glass cloth, etc.

[1022] An organic sol of PTFE can also be prepared from the above aqueous dispersion. The above organic sol can contain the above PTFE and an organic solvent, and as the above organic solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, an amide-based solvent, an ester-based solvent, an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent can be cited, and N-methyl-2-pyrrolidone, dimethylacetamide, etc. can be appropriately used. The preparation of the above organic sol can be performed, for example, by the method described in International Publication No. 2012 / 002038.

[1023] The above aqueous dispersion of PTFE or the above fine powder of PTFE is also preferably used as a processing aid. When used as a processing aid, by mixing the above aqueous dispersion or the above fine powder in a base polymer, etc., the melt strength at the time of melt processing of the base polymer can be improved, and the mechanical strength, the electrical properties, the flame retardancy, the dripping resistance at the time of combustion, the slidability of the obtained polymer can be improved.

[1024] The above aqueous dispersion of PTFE or the above fine powder of PTFE is also preferably used as a binder for batteries, a dust-proofing use.

[1025] The fine powder of PTFE obtained by the production method using the present application can also obtain an un-baked tape (green tape).

[1026] In addition, the above aqueous dispersion of PTFE or the above fine powder of PTFE is also preferably used as a processing aid after being compounded with a resin other than PTFE. The above aqueous dispersion or the above fine powder is, for example, suitable as a raw material of PTFE described in Japanese Patent Application Laid-Open No. 11-49912, U.S. Patent No. 5804654, Japanese Patent Application Laid-Open No. 11-29679, Japanese Patent Application Laid-Open No. 2003-2980. The processing aid using the above aqueous dispersion or the above fine powder is not inferior at all to the processing aids described in the above publications.

[1027] The above aqueous dispersion of PTFE is also preferably made into a co-precipitated powder by mixing with an aqueous dispersion of a melt-processable fluororesin and allowing it to be co-precipitated. The above co-precipitated powder is suitable as a processing aid.

[1028] As the above melt-processable fluororesin, for example, FEP, PFA, ETFE, an ethylene / TFE / HFP copolymer [EFEP], etc. can be cited, and FEP is preferable among them.

[1029] The aqueous dispersion described above also preferably contains the melt-processable fluororesin described above. As the melt-processable fluororesin, for example, FEP, PFA, ETFE, EFEP, etc. can be given. The aqueous dispersion described above containing the melt-processable fluororesin can be used as a coating material. The melt-processable fluororesin described above enables the particles of PTFE described above to be sufficiently fused to each other, and thus enables the film-forming property to be improved and the resulting coating film to exhibit gloss.

[1030] The non-fluorine-containing resin to which the co-coagulum powder described above is added can be in the form of a powder, can be in the form of a granule, or can be in the form of an emulsion. From the viewpoint of sufficiently mixing the respective resins, the addition described above is preferably performed while imparting a shear force using a publicly known method such as extrusion kneading, roll kneading, etc.

[1031] The aqueous dispersion of PTFE described above is also preferably used as a dust suppressing treatment agent. The dust suppressing treatment agent described above can be used in a method in which a dusting substance is mixed, and compression-shear is applied to the mixture at a temperature of 20 to 200°C, thereby fibrillating PTFE and suppressing the dust of the dusting substance; a method described in, for example, Japanese Patent No. 2827152, Japanese Patent No. 2538783, etc.

[1032] The aqueous dispersion of PTFE described above can be appropriately used in, for example, a dust suppressing treatment agent composition described in International Publication No. 2007 / 004250, and can also be appropriately used in a dust suppressing treatment method described in International Publication No. 2007 / 000812.

[1033] The dust suppressing treatment agent described above is suitably used in the fields of building materials, soil stabilizing materials, solidifying materials, fertilizers, land filling treatment of incineration ash and harmful substances, explosion prevention, cosmetics, sand for pet excretion represented by cat litter, etc.

[1034] The aqueous dispersion of PTFE described above is also preferably used as a raw material for obtaining a PTFE fiber by a dispersion spinning method. The dispersion spinning method described above refers to a method in which an aqueous dispersion of PTFE described above is mixed with an aqueous dispersion of a base polymer, the mixture is subjected to extrusion processing to form an intermediate fiber structure, and the intermediate fiber structure is subjected to firing, thereby decomposing the base polymer and performing sintering of PTFE particles, to obtain a PTFE fiber.

[1035] A high molecular weight PTFE powder obtained by polymerization has stretchability and non-melt-processability, and is also useful as a raw material for a stretched body (porous body).

[1036] In the case of the stretched body being a film (PTFE stretched film or PTFE porous film), stretching can be performed by a known PTFE stretching method. By performing stretching, the high molecular weight PTFE is easily fibrillated to become a PTFE porous body (film) composed of nodules and fibers.

[1037] Preferably, the paste extrudate in the form of a sheet or a rod is roll-stretched in the extrusion direction, whereby a uniaxially stretched film can be obtained.

[1038] Further, by stretching in the width direction using a tenter or the like, a biaxially stretched film can also be obtained.

[1039] It is also preferable to perform a semi-baking treatment before stretching.

[1040] The PTFE stretched body is a porous body having a high porosity, and is suitably used as a filter material for various microporous filters such as air filters, liquid filters, and the like, a support material for polymer electrolyte membranes, and the like.

[1041] In addition, it is also useful as a raw material for products used in the fields of fibers, medical fields, electrochemical fields, sealing material fields, air filtration fields, ventilation / inner pressure adjustment fields, liquid filtration fields, general consumable material fields, and the like.

[1042] The following illustrates specific uses.

[1043] Electrochemical fields

[1044] Dielectric material prepreg, EMI shielding material, heat transfer material, and the like. More specifically, printed circuit substrates, electromagnetic shielding materials, insulating heat transfer materials, insulating materials, and the like.

[1045] Sealing material fields

[1046] Gaskets, gasketing, pump diaphragms, pump tubes, sealing materials for aircraft, and the like.

[1047] Air filtration fields

[1048] 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), filters with adsorbents (for HDD assembly), air vent filters with adsorbents (for HDD assembly), air vent filters (for HDD assembly and the like), filters for vacuum cleaners (for vacuum cleaners), general-purpose multilayer felt materials, cartridge filters for GT (for GT-oriented interchangeable products), cooling filters (for electronic device housings), and the like.

[1049] Ventilation / inner pressure adjustment fields

[1050] Freeze-drying materials for freeze-drying containers and the like, automotive air exchange materials facing electronic circuits or lamps, container applications facing container lids and the like, protective air exchange applications facing electronic devices including small terminals such as input tablet terminals or mobile phone terminals, and the like, medical air exchange applications, and the like.

[1051] Liquid filtration field

[1052] Semiconductor liquid filtration filters (for semiconductor manufacturing), hydrophilic PTFE filters (for semiconductor manufacturing), filters facing chemical drugs (for liquid medicine processing), filters for pure water manufacturing lines (for pure water manufacturing), filters for backwash-type liquid filtration (for industrial wastewater treatment), and the like.

[1053] General consumable material field

[1054] Clothing, cable guide tubes (movable electric wires facing motorcycles), motorcycle clothing, pouring gaskets (medical aids), vacuum cleaner filters, bagpipes (musical instruments), cables (guitar signal cables and the like), strings (for stringed instruments), and the like.

[1055] Fiber field

[1056] PTFE fibers (fiber materials), sewing threads (textiles), woven threads (textiles), ropes, and the like.

[1057] Medical field

[1058] Implants (stretching products), artificial blood vessels, catheters, general surgery (tissue reinforcement materials), head and neck products (dura mater substitutes), oral health (tissue regeneration medicine), plastic surgery (tapes), and the like.

[1059] In the above Af, when the polymerization unit based on TFE is greater than 80 mol%, a polymerization unit based on a monomer other than TFE can be included. As the monomer other than TFE, the same as described in the above manufacturing method of the present application.

[1060] It is one way that it is a fluoropolymer segment in which a monomer unit from a monomer represented by General Formula (1) and / or General Formula (2) as the above polymerization unit based on a monomer other than TFE is randomly copolymerized.

[1061] As the above monomer represented by General Formula (1) and / or General Formula (2), the same as the monomer described in the above manufacturing method of the present application.

[1062] In this case, the polymerization units based on TFE in the above Af are preferably more than 80 mol% and less than 100 mol%. In the above Af, the polymerization units based on TFE preferably include 81 mol% or more, more preferably include 90 mol% or more, further preferably include more than 90 mol%, further more preferably include 95 mol% or more, particularly preferably include 99 mol% or more.

[1063] In the case where the above Af is a fluorine-containing polymer segment resulting from random copolymerization of monomer units from TFE and monomer units from the monomer represented by General Formula (1) and / or General Formula (2), the above fluorine-containing polymer is a copolymer of TFE and the monomer represented by General Formula (1) and / or General Formula (2), and examples thereof include melt-processable fluororesins such as a TFE-HFP copolymer (FEP), a TFE-perfluoro(alkyl vinyl ether) copolymer (PFA), an ethylene-TFE copolymer (ETFE), a TFE / VDF copolymer, and the like.

[1064] It can also be a modified PTFE composed of TFE and a monomer other than TFE (a modifying monomer). In this case, the monomer other than TFE is preferably 1 mass% or less.

[1065] The preferred monomer composition (mass%) of the above FEP is TFE:HFP = (80 to 95):(5 to 20), more preferably (85 to 92):(8 to 15). As the above FEP, a perfluoro(alkyl vinyl ether) can also be further used as a third component, and is modified within a range of 0.1 to 2 mass% of the total monomers.

[1066] The above FEP can be supplied to, for example, the manufacture of coated materials for electric wires, foamed electric wires, electric cables, conductive wires, and the like, pipes, films, sheets, filaments, and the like, and various molded products.

[1067] The preferred monomer composition (mol%) of the above PFA is TFE:perfluoro(alkyl vinyl ether) = (90 to 99.7):(0.3 to 10), more preferably (97 to 99):(1 to 3). As the above perfluoro(alkyl vinyl ether), a monomer represented by the formula: CF2=CFORf 4 (In the formula, Rf 4 is a perfluoroalkyl group having 1 to 6 carbon atoms).

[1068] Various shaped articles can be obtained from the aforementioned PFA. If examples of the shaped articles are given, there are sheets, films, gaskets, round bars, square bars, pipe blanks, pipes, round grooves, square grooves, tanks, wafer carriers, wafer cassettes, beakers, filter housings, flowmeters, pumps, valves, faucets, connectors, nuts, electric wires, heat-resistant electric wires, and the like. Among these, pipes, pipe blanks, tanks, connectors, and the like are particularly suitably used for various chemical reaction apparatuses, semiconductor manufacturing apparatuses, and the like that require impermeability of a chemical liquid, and for acid or alkali chemical liquid supply apparatuses and the like.

[1069] Furthermore, the PFA can be dissolved or dispersed in an organic solvent, alone or in combination with polyether sulfone, polyamide-imide, polyimide, metal powder, and the like, as needed, to obtain a primer coating composition. The primer coating composition can also be used in a coating method for coating a fluororesin on a metal surface, the method including applying the primer coating composition to the metal surface, applying a melt-processible fluororesin composition to the primer coating layer thus formed, and performing sintering of the melt-processible fluororesin composition layer together with the primer coating layer.

[1070] The preferred monomer composition (mole %) of the aforementioned ETFE is TFE: ethylene = (80 to 99): (20 to 1). As the aforementioned ETFE, a third monomer can be further used to modify in a range of 0 to 20 mass % of the total monomers. Preferably, TFE: ethylene: third monomer = (80 to 94): (19 to 2): (1 to 10). As the aforementioned third monomer, perfluorobutylethylene, perfluorobutylethylene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-l-octene, 2,3,3,4,4,5,5-heptafluoro-l-pentene (CH2=CFCF2CF2CF2H), 2-trifluoromethyl-3,3,3-trifluoropropene ((CF3)2C=CH2) are preferred.

[1071] The aforementioned ETFE can also be extrusion-molded to produce a sheet. For example, ETFE powder or a pellet of ETFE can be melted, continuously extruded from a die, and cooled to obtain a sheet-shaped shaped article. An additive can be added to the ETFE.

[1072] As the additive, a well-known substance can be suitably used. As specific examples, ultraviolet absorbers, light stabilizers, antioxidants, infrared absorbers, flame retardants, flame retardant fillers, organic pigments, inorganic pigments, dyes, and the like can be given. From the aspect of excellent weather resistance, inorganic additives are preferred.

[1073] The content of the additive in the aforementioned ETFE sheet is preferably 20 mass % or less, and particularly preferably 10 mass % or less, relative to the total mass of the ETFE sheet.

[1074] The sheet of the above-mentioned ETFE is excellent in mechanical strength and appearance, and is thus suitable as a film material (roofing material, ceiling material, outer wall material, inner wall material, coating material, etc.) for a membrane structure building (sports facilities, horticultural facilities, atrium, etc.).

[1075] In addition, the above-mentioned ETFE is not only useful as a film material for a membrane structure building, but is also useful in, for example, the following materials: outdoor-use board (soundproof wall, wind fence, wave fence, garage roof, shopping center, sidewalk of a pedestrian mall, roofing material), anti-glass scattering film, heat- and water-resistant sheet, building material, etc. (tent material for a tent warehouse, film material for sunshade, partial roofing material for lighting, window material instead of glass, film material for fireproof spacing, window shade, outer wall reinforcement, waterproof film, smokeproof film, fireproof transparent partition, road reinforcement, interior decoration (lighting, wall, shutter, etc.), exterior decoration (curtain, signboard, etc.), etc.), living and leisure goods (fishing rod, racket, golf club, screen, etc.), automobile material (canopy, damping material, vehicle body, etc.), aircraft material, ship material, housing of an electric appliance, tank, inner wall of a container, filter, film material for construction, electronic material (printed board, wiring board, insulating film, anti-sticking film, etc.), surface material of a solar cell module, mirror protection material for solar power generation, surface material of a solar water heater, etc.

[1076] The preferable monomer composition (mole %) of the above-mentioned TFE / VDF copolymer is TFE:VDF = (81 to 90):(10 to 19). As the TFE / VDF copolymer, a 3rdmonomer can be further used to modify in the range of 0 to 10 mole % of the total monomers.

[1077] As the above-mentioned 3rdmonomer, the following monomers are preferable:

[1078] Formula: CX 11 X 12 =CX 13 (CX 14 X 15 ) n11 X 16

[1079] (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. TFE and VDF are excluded therefrom) or

[1080] Formula: CX 21 X 22 =CX 23 -O(CX 24 X 25 ) n21 X 26

[1081] (In the formula, X 21 ~X 26 identical or different, represent H, F or Cl, and n21 represents an integer of 0 to 8.

[1082] In addition, the third monomer can be a non-fluorine-containing ethylenic monomer. As the above non-fluorine-containing ethylenic monomer, from the viewpoint of maintaining heat resistance and chemical resistance, it is preferable to select an ethylenic monomer having 6 or less carbon atoms. Examples 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, methacrylic acid, and the like.

[1083] The obtained TFE / VDF copolymer can be subjected to amidation treatment by contact with aqueous ammonia, ammonia gas, or a nitrogen compound that generates ammonia.

[1084] The above TFE / VDF copolymer is also preferably used as a raw material for obtaining a TFE / VDF copolymer fiber by a spin-drawing method. The above spin-drawing method refers to a method in which a TFE / VDF copolymer is melt-spun and then cooled and solidified to obtain an undrawn yarn, and then the undrawn yarn is caused to travel in a heated cylindrical body to be drawn, thereby obtaining a TFE / VDF copolymer fiber.

[1085] The above TFE / VDF copolymer can also be dissolved in an organic solvent to obtain a solution of the above TFE / VDF copolymer. As the above organic solvent, for example, nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylformamide, and the like; ketone-based solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and the like; ester-based solvents such as ethyl acetate, butyl acetate, and the like; ether-based solvents such as tetrahydrofuran, dioxane, and the like; and mixed solvents of these, and the like, general-purpose organic solvents having low boiling points, can be mentioned. The above solution can be used as a binder for batteries.

[1086] It is also preferable to coat the above aqueous dispersion of the TFE / VDF copolymer on a porous substrate composed of a polyolefin resin and use it as a composite porous film. It is also preferable to disperse inorganic particles and / or organic particles in the aqueous dispersion and coat them on a porous substrate and use it as a composite porous film. The composite porous film thus obtained can be used as a separator for lithium secondary batteries and the like.

[1087] The powder of the melt-processable fluororesin described above is suitable for use as a powder paint. When the powder paint composed of the powder of the melt-processable fluororesin described above is applied to a substrate, a coating film with a smooth surface can be obtained. The powder of the melt-processable fluororesin having an average particle diameter of 1 μm or more and less than 100 μm is particularly suitable as a powder paint used in electrostatic coating, and the powder of the melt-processable fluororesin having an average particle diameter of 100 μm or more and 1000 μm or less is particularly suitable as a powder paint used in spin coating or spin molding.

[1088] The powder of the melt-processable fluororesin described above can be produced by a method in which the melt-processable fluororesin obtained by the production method of the present application described above is dried and powderized.

[1089] In the case where the Af is a polymer segment resulting from random copolymerization of TFE and a monomer other than TFE, the resulting fluorine-containing polymer can be a modified PTFE containing 99.0% by mass or more of polymer units based on TFE and 1.0% by mass or less of polymer units based on the modifying monomer other than TFE.

[1090] The total amount of the modifying monomer described above is preferably in the range of 0.00001 to 1.0% by mass with respect to the fluorine-containing polymer obtained in the process (ii). As the lower limit of the total amount, 0.0001% by mass is more preferable, 0.001% by mass is further preferable, 0.005% by mass is further more preferable, and 0.009% by mass is particularly preferable. As the upper limit, 0.90% by mass is preferable, 0.50% by mass is more preferable, 0.40% by mass is further preferable, 0.30% by mass is further more preferable, and 0.10% by mass is especially further preferable.

[1091] As the modifying monomer described above, for example, the monomers represented by the general formula (1) and the general formula (2) described above can be mentioned, and at least one selected from the group consisting of HFP, VDF, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), perfluoro-fluorosulfonyl vinyl ether, ethylene, an N-vinyl amide compound, N-vinyl pyrrolidone, and vinyl acetate is particularly preferable.

[1092] In the fluorine-containing polymer of the present application, the number average molecular weight is preferably 1000 or more from the viewpoint of reducing environmental load. The number average molecular weight of the fluorine-containing polymer of the present application is more preferably 3000 or more, further preferably 5000 or more, and particularly preferably 10000 or more.

[1093] With respect to the number average molecular weight described above, for example, in the case of PTFE, the number average molecular weight is preferably 1000 or more and 10000 or more, more preferably 3000 or more and 10000 or more, and further more preferably 5000 or more and 10000 or more, according to the solid content of the fluorine-containing polymer. 19The ratio of the peak integral value of the CF2 chain from the TFE monomer chain to the peak integral value of the chain transfer agent fragment from the polymer end obtained by F-NMR measurement estimates the polymerization degree n, from which the number average molecular weight described above is calculated. The number average molecular weight of the polymer can be calculated as the product (m x n) of the molecular weight m of the monomer and the polymerization degree n.

[1094] Regarding the number average molecular weight described above, for example, in the case of a polymer that can be dissolved in a solvent, it can be the number average molecular weight obtained by GPC measurement.

[1095] The present application also relates to a composition characterized by comprising a fluorine-containing polymer represented by the following formula:

[1096] Af-CRP

[1097] (In the formula, Af is a fluorine-containing polymer segment containing more than 80 mol% of polymerization units based on TFE. CRP is any one of the following formulas (CRP1) to (CRP5)).

[1098] Formula (CRP1):

[1099] -SC(S)Z c11

[1100] (In the formula, Z c11 is an alkyl group or an aryl group.)

[1101] Formula (CRP2):

[1102] -SC(S)SZ c12

[1103] (In the formula, Z c12 is an alkyl group or an aryl group.)

[1104] Formula (CRP3):

[1105] -SC(S)SR c11

[1106] (In the formula, R c11 is a monovalent organic group.)

[1107] Formula (CRP4):

[1108] -SC(S)NZ c13 2

[1109] (In the formula, Z c13 (i) is independently an alkyl group, an aryl group, or a 4-pyridyl group, or (ii) is a group that is bonded to each other and forms a heterocyclic ring together with the N atom in the formula.)

[1110] Formula (CRP5):

[1111] -SC(S)OZ c14

[1112] (In the formula, Z c14 is an alkyl group or an aryl group.)

[1113] The fluorine-containing polymer in the composition of the present application is the same as the fluorine-containing polymer of the present application described above.

[1114] The fluorine-containing polymer described above can be produced by the production method of the present application described above.

[1115] The composition of the present application preferably further contains the surfactant described above. As the surfactant described above, the surfactant used in the production method of the present application described above can be given. The surfactant described above can be a fluorine-containing surfactant or a hydrocarbon-based surfactant, and is preferably a hydrocarbon-based surfactant.

[1116] The composition of the present application can be an aqueous dispersion, can be a powder, or can be a pellet. The aqueous dispersion can be a dispersion in which polymerization is completed, or can be a substance obtained by processing the dispersion in which polymerization is completed. For example, a nonionic surfactant or the like can be added for the purpose of mechanical stability, storage stability, or the like. In the case where the nonionic surfactant described above is added, the amount of addition is preferably 0.5 to 25% by mass with respect to the fluorine-containing polymer described above. The lower limit of the amount of addition described above is more preferably 1% by mass, and further preferably 3% by mass. The upper limit is more preferably 20% by mass, further preferably 15% by mass, and particularly preferably 10% by mass.

[1117] The aqueous dispersion is a dispersion system in which an aqueous medium is used as a dispersion medium, and the fluorine-containing polymer described above is used as a dispersed substance. The aqueous medium described above is not particularly limited as long as it is a liquid containing water, and can contain, for example, an organic solvent such as an alcohol, an ether, a ketone, a paraffin, or the like, in addition to water.

[1118] The lower limit of the content of the surfactant described above in the composition described above is preferably 10 ppb, more preferably 100 ppb, further preferably 1 ppm, further more preferably 10 ppm, and particularly preferably 50 ppm, with respect to the fluorine-containing polymer described above. The upper limit is preferably 100000 ppm, more preferably 50000 ppm, further preferably 10000 ppm, and particularly preferably 5000 ppm, with respect to the fluorine-containing polymer (1).

[1119] The present application also relates to a molded body obtained by molding the composition described above. The composition described above used in the molding is preferably a powder or a pellet.

[1120] The molding method is not particularly limited, and for example, compression molding, extrusion molding, transfer molding, injection molding, blow molding, rotational molding, slush molding, electrostatic coating, or the like can be given.

[1121] The shape of the above-mentioned molded body is not particularly limited, and examples thereof include a hose, a pipe blank, a pipe, a sheet, a seal, a gasket, a packing, a film, a tank, a roll, a bottle, a container, and the like.

[1122] Further, the present application also provides a method for producing a fluoropolymer (hereinafter also referred to as "2nd production method of the present application"), characterized by comprising: a polymerization step of polymerizing TFE in an aqueous medium in the presence of an initiator, a chain transfer agent, and a surfactant to obtain a fluoropolymer containing more than 80 mol% (preferably more than 90 mol%) of polymer units based on TFE; and a block polymerization step of block copolymerizing a monomer other than TFE in an aqueous medium containing the fluoropolymer obtained in the polymerization step; the above-mentioned chain transfer agent being at least one selected from the group consisting of a dithioester compound, a dithiourethane compound, a trithiocarbonate compound, and a xanthate compound.

[1123] In the 2nd production method of the present application, the initiator, the chain transfer agent, the surfactant, the aqueous medium, and the monomer other than TFE are the same as described in the production method of the present application. Further, the above-mentioned polymerization step is the same as in the production method of the present application. By the above-mentioned polymerization step, a polymer having a CRP at the terminal can be obtained as described in the fluoropolymer of the present application, and thus the block copolymerization of the monomer other than TFE can be performed.

[1124] In the 2nd production method of the present application, the polymerization step can be performed once, or two or more times. By performing two or more times, a block copolymer having two or more blocks can be produced.

[1125] In the 2nd production method of the present application, the above-mentioned polymerization step and the block polymerization step can be performed continuously, or the polymer obtained in the above-mentioned polymerization step can be recovered, the recovered polymer can be added to the aqueous medium, and then the monomer other than TFE can be added to perform polymerization.

[1126] The temperature of the above-mentioned block polymerization step is not particularly limited as long as it is a temperature at which block copolymerization can be performed, and can be, for example, 0 to 150°C. It is preferably 20 to 130°C, and more preferably 40 to 110°C.

[1127] The pressure of the above-mentioned block polymerization step is not particularly limited as long as it is a pressure at which block copolymerization can be performed, and can be, for example, 0 to 9.8 MPaG. It is preferably 0.2 to 6.0 MPaG, and more preferably 0.5 to 3.0 MPaG.

[1128] The concentration of the monomer other than TFE with respect to the aqueous medium in the above block polymerization step is preferably 0.1 to 20 mol / liter. More preferably, it is 0.3 to 18 mol / liter, and further preferably, it is 0.5 to 15 mol / liter.

[1129] The above block polymerization step can be performed once, or two or more times. By performing two or more times, a block copolymer having two or more blocks can be produced.

[1130] As the fluorine-containing polymer obtained by the second production method of the present application, for example, the second fluorine-containing polymer of the present application described later and the like can be given.

[1131] The present application also provides a fluorine-containing polymer (hereinafter also referred to as "the second fluorine-containing polymer of the present application") composed of a block A containing more than 80 mol% of polymerized units based on TFE, and a block B containing polymerized units based on a monomer other than TFE. The above monomer other than TFE is not particularly limited, and preferably, it is the monomer represented by the above general formula (1) and / or (2).

[1132] The above block A contains more than 80 mol% of monomer units from TFE. The block A preferably contains more than 90 mol% of monomer units from TFE, and more preferably, it is composed of only polymerized units based on TFE. The above block A is preferably a polymer block composed of a TFE homopolymer (PTFE), and all the features of the above PTFE can be adopted.

[1133] The segment B can contain a polymerization unit based on a monomer other than TFE, and preferably contains a polymerization unit based on a monomer represented by General Formula (1) and / or General Formula (2), and is particularly preferably at least one selected from the group consisting of HFP, CTFE, VDF, fluoroethylene, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl ester, (meth)acrylate, olefin, non-fluorine-containing monomer having an amide bond, fluoroalkyl ethylene, and fluorine-containing acrylate monomer, more preferably at least one selected from the group consisting of HFP, CTFE, VDF, fluoroethylene, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl ester, (meth)acrylate, acrylamide, olefin, vinylamide, fluoroalkyl ethylene, and fluorine-containing acrylate monomer, further preferably at least one selected from the group consisting of HFP, CTFE, VDF, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl ester, (meth)acrylate, N-acrylamide compound, olefin, N-vinylamide compound, N-vinyl lactam compound, fluoroalkyl ethylene, and fluorine-containing acrylate monomer, further more preferably at least one selected from the group consisting of HFP, VDF, perfluoro(methyl vinyl ether), perfluoro fluorosulfonyl vinyl ether, ethylene, N-vinylamide compound, N-vinyl lactam compound, and vinyl acetate, particularly preferably at least one selected from the group consisting of HFP, VDF, perfluoro(methyl vinyl ether), perfluoro fluorosulfonyl vinyl ether, ethylene, N-vinylamide compound, N-vinyl pyrrolidone, and vinyl acetate.

[1134] As the polymer constituting the above-mentioned segment B, a polymer containing a polymerization unit based on a monomer other than TFE, and preferably containing a polymerization unit based on a monomer represented by General Formula (1) and / or General Formula (2), is exemplified, such as polyvinyl acetate, polyvinylamide such as poly(N-vinyl pyrrolidone), polyfluoroolefin such as PVDF, and the like.

[1135] The second fluorine-containing polymer of the present application contains a segment A and a segment B. The second fluorine-containing polymer of the present application preferably contains the following formula:

[1136] -A-L-B-

[1137] (Formula in which A is the segment A, B is the segment B, and L represents a linking group).

[1138] The above-mentioned L can be a single bond or a divalent organic group. As the divalent organic group in L, an alkylene group, an oxyalkylene group, and the like can be given.

[1139] The above-mentioned L is preferably a single bond.

[1140] The second fluorine-containing polymer of the present application preferably comprises an -A-B- structure in which the above-mentioned segment A and segment B are bonded via a single bond.

[1141] The bonding of segment A and segment B via a single bond means that a polymerization unit constituting the end portion of segment A (for example, a polymerization unit from TFE) is directly bonded to a polymerization unit constituting the end portion of segment B (for example, a polymerization unit based on the monomer represented by General Formula (1) and / or General Formula (2)). Such constitution can be achieved by the second production method of the present application.

[1142] In the second fluorine-containing polymer of the present application, the -A-L-B- structure can be present in at least 1, 2 or more, or 3 or more. That is, in the third fluorine-containing polymer of the present application, at least 1 segment A and at least 1 segment B can be bonded via L (preferably a single bond), and -A-L-B- can be repeated 2 or more times, or can have a structure repeated 3 or more times. For example, it can be constituted by -A-L-B-, -B-L-A-, -A-L-B-L-A-, -B-L-A-L-B-, -A-L-B-L-A-L-B-, -B-L-A-L-B-L-A-, and the like.

[1143] In the second fluorine-containing polymer of the present application, the mass ratio (A / B) of the above-mentioned segment A and segment B can be 99 / 1 to 1 / 99.

[1144] The second fluorine-containing polymer of the present application can have both properties of segment A comprising a monomer unit based on a monomer from TFE, and segment B comprising a monomer unit based on a monomer represented by General Formula (1) and / or General Formula (2). Such fluorine-containing polymer can be expected to be used, for example, as a compatibilizer, an adhesive for compounding fluororesins.

[1145] In addition, the second fluorine-containing polymer of the present application can also be used for the uses of each of the fluorine-containing polymers described in the first and second fluorine-containing polymers of the present application.

[1146] Examples

[1147] The present application will be described in more detail by citing examples, but the present application is not limited to these examples.

[1148] In the examples, sodium 10-oxoundecyl sulfate represented by the following formula was used as a surfactant.

[1149] [Chemical Formula 55]

[1150]

[1151] Example 1

[1152] Into an autoclave were put water 550 g, 10-oxo undecyl sodium sulfate 0.019 g, paraffin 30 g, O-ethyl S-(1-methoxycarbonyl ethyl) dithiocarbonate 0.10 g, and the system was replaced with nitrogen and depressurized. The system was replaced with TFE, and the temperature was raised to 70°C. Then ammonium persulfate (APS) 0.11 g was supplied to initiate polymerization. The polymerization was carried out under stirring at a polymerization pressure of 0.83 MPa, and TFE was continuously supplied to compensate for the pressure drop during polymerization. After the polymerization was completed, the fluorine-containing polymer dispersion was dried to obtain a dried fluorine-containing polymer 3.0 g. The monomer composition ratio was estimated from the ratio of the infrared absorbance at 982 cm"1 to that at 935 cm"1 in FT-IR measurement of the dried fluorine-containing polymer, and the ratio was multiplied by 0.3 to obtain TFE / HFP: 94 / 6 (mole %). 19 F-NMR measurement (high-speed MAS method) showed that when the peak from the CF2 chain of the TFE monomer chain was taken as a reference (-CF2CF2CF2 = -120 ppm), a peak from -CF2-S- was observed at -85 ppm, and thus it was confirmed that the chain transfer agent fragment A (-SC(S)OC2H5) was introduced at the end of the polymer. In addition, fragment B (-CF2H) was also confirmed. The polymerization degree estimated from the ratio of the peak integral value from the CF2 chain to the peak integral value of fragments A+B was 249.

[1153] Example 2

[1154] Into an autoclave were put water 550 g, 10-oxo undecyl sodium sulfate 0.019 g, paraffin 30 g, O-ethyl S-(1-methoxycarbonyl ethyl) dithiocarbonate 0.10 g, and the system was replaced with nitrogen and depressurized. The system was replaced with TFE / VDF mixed monomers 91 / 9 (mole %), and the temperature was raised to 70°C. Then ammonium persulfate (APS) 0.11 g was supplied to initiate polymerization. The polymerization was carried out under stirring at a polymerization pressure of 0.90 MPa, and TFE / VDF mixed monomers 91 / 9 (mole %) were continuously supplied to compensate for the pressure drop during polymerization. After the polymerization was completed, the fluorine-containing polymer dispersion was dried to obtain a dried fluorine-containing polymer 3.3 g. The monomer composition ratio was estimated from F-NMR measurement and elemental analysis, and the monomer composition ratio was TFE / VDF: 92 / 8 (mole %). 19 F-NMR measurement and elemental analysis estimated the monomer composition ratio to be TFE / VDF: 92 / 8 (mole %).

[1155] Example 3

[1156] In Example 1, except that 0.3 g of HFP was added, the polymerization was carried out in the same manner as in Example 1. After the obtained fluorine-containing polymer dispersion was dried, a dried fluorine-containing polymer 3.1 g was obtained. The monomer composition ratio was estimated from the ratio of the infrared absorbance at 982 cm"1 to that at 935 cm"1 in FT-IR measurement of the dried fluorine-containing polymer, and the ratio was multiplied by 0.3 to obtain TFE / HFP: 94 / 6 (mole %). -1 -1 The monomer composition ratio estimated from the ratio of the infrared absorbance at 982 cm"1 to that at 935 cm"1 in FT-IR measurement of the dried fluorine-containing polymer, and the ratio was multiplied by 0.3 to obtain TFE / HFP: 94 / 6 (mole %).

[1157] Example 4​

[1158] In Example 1, the polymerization was carried out in the same manner as in Example 1 except that 0.2 g of perfluoro(methyl vinyl ether) (PMVE) was added. After the obtained fluorine-containing polymer dispersion was dried, a dried fluorine-containing polymer 3.0 g was obtained. The monomer composition ratio was estimated from the integral value of the peak of CF2 chain from TFE monomer chain (CF2CF2CF2 = -120 ppm) and the integral value of the peak of CF from PMVE (-52 ppm) by F-NMR measurement to be TFE / PMVE: 95 / 5 (mole %). 19 F-NMR measurement, the monomer composition ratio was estimated from the integral value of the peak of CF2 chain from TFE monomer chain (CF2CF2CF2 = -120 ppm) and the integral value of the peak of CF from PMVE (-52 ppm) to be TFE / PMVE: 95 / 5 (mole %).

[1159] Example 5

[1160] In Example 1, the polymerization was carried out in the same manner as in Example 1 except that 0.3 g of perfluoro(propyl vinyl ether) (PPVE) was added. After the obtained fluorine-containing polymer dispersion was dried, a dried fluorine-containing polymer 3.1 g was obtained. The monomer composition ratio was estimated from the integral value of the peak of CF2 chain from TFE monomer chain (CF2CF2CF2 = -120 ppm) and the integral value of the peak of CF from PPVE (-52 ppm) by F-NMR measurement to be TFE / PPVE: 95 / 5 (mole %). 19 F-NMR measurement, the monomer composition ratio was estimated from the integral value of the peak of CF2 chain from TFE monomer chain (CF2CF2CF2 = -120 ppm) and the integral value of the peak of CF from PMVE (-52 ppm) to be TFE / PMVE: 95 / 5 (mole %).

Claims

1. A method for producing a fluorine-containing polymer, characterized in that: The production method comprises a polymerization step: in the presence of an initiator, a chain transfer agent and a surfactant containing no fluorine atoms, tetrafluoroethylene is polymerized in an aqueous medium to obtain a fluorine-containing polymer containing more than 90 mol % of tetrafluoroethylene-based polymer units, wherein the chain transfer agent is added in a single addition. The chain transfer agent is at least one selected from the group consisting of dithioester compounds, dithiocarbamate compounds, trithiocarbonate compounds, and xanthate compounds.

2. The manufacturing method according to claim 1, wherein The fluoropolymer comprises only polymerized units based on tetrafluoroethylene.

3. The manufacturing method according to claim 1 or 2, wherein: The fluoropolymer further comprises polymerized units based on monomers other than tetrafluoroethylene.

4. The manufacturing method according to claim 3, wherein: The monomer other than tetrafluoroethylene is at least one selected from the group consisting of a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2), General formula (1): CF2=CR p R q In the general formula (1), R p H or F; R q -Cl, -CF3, -R a 、-COOR b 、-OCOR c 、-CONR d 2. -CN, -COR e 、-Rf a 、-ORf b ; R a 、R b 、R c 、R d and R e The same or different, is H or a substituent; Rf a is a fluorinated alkyl group or a fluorinated vinyl group which may have a substituent and may contain an oxygen atom between carbon atoms; Rf b is a fluorinated alkyl group; R p and R q can bond with each other to form rings; General formula (2): CH2=CR s R t In the general formula (2), R s R g , CF3 or F; R t -Cl, -R h 、-COOR i 、-OCOR j 、-CONR k 2. -CN, -COR m 、Rf c ; R g and R h are the same or different and are H or a hydrocarbon group or a heterocyclic group which may have a substituent; R i 、R j 、R k and R m The same or different, is H or a substituent; Rf c is a fluorinated alkyl group, a fluorinated vinyl group, or a fluorinated alkoxy group which may have a substituent and may contain an oxygen atom between carbon atoms; R s and R t They may be bonded to each other to form a ring.

5. The manufacturing method according to claim 3 or 4, wherein: The monomer other than tetrafluoroethylene is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl esters, (meth)acrylates, acrylamide, olefins, vinylamide, fluoroalkylethylenes and fluorine-containing acrylate monomers.

6. The production method according to any one of claims 1 to 5, wherein The chain transfer agent is a xanthate compound.

7. The production method according to any one of claims 1 to 6, wherein The chain transfer agent is O-ethyl S-(1-methoxycarbonylethyl)dithiocarbonate.

8. The production method according to any one of claims 1 to 7, wherein In the polymerization step, the concentration of the chain transfer agent relative to the aqueous medium is 0.1×10 -3 mol / L~0.01 mol / L.

9. A fluorine-containing polymer, characterized in that The fluoropolymer is obtained by the production method according to any one of claims 1 to 8, and is represented by the formula: Af-CRP, wherein Af is a fluoropolymer segment containing more than 90 mol% of tetrafluoroethylene-based polymer units; CRP is any one of the following formulas (CRP1) to (CRP5), Formula (CRP1): -SC(S)Z c11 Where Z c11 is an alkyl group or an aryl group; Formula (CRP2): -SC(S)SZ c12 Where Z c12 is an alkyl group or an aryl group; Formula (CRP3): -SC(S)SR c11 Where R c11 is a monovalent organic group; Formula (CRP4): -SC(S)NZ c13 2 Where Z c13 (i) are independently alkyl, aryl or 4-pyridyl, or (ii) are groups that are bonded to each other and together with the nitrogen atom in the formula form a heterocyclic ring; Formula (CRP5): -SC(S)OZ c14 Where Z c14 is an alkyl group or an aryl group.

10. The fluorine-containing polymer according to claim 9, wherein In the formula, CRP is represented by formula (CRP5).

11. The fluorine-containing polymer according to claim 9, wherein The fluorine-containing polymer is represented by the formula: Bf-CRP, wherein Bf is a fluorine-containing polymer segment containing only tetrafluoroethylene-based polymerization units; and CRP is the same as above.

12. The fluorinated polymer according to any one of claims 9 to 11, wherein The number average molecular weight of the fluorine-containing polymer is 3,000 or more.

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