Composition and method for producing same

Abstract

The present application relates to compositions and methods of making the same. Provided is a composition containing polytetrafluoroethylene, a polymer (I) containing a polymerization unit (I) based on a monomer represented by general formula (I), a nonionic surfactant, and an aqueous medium, the content of the polytetrafluoroethylene in the composition being 10% by mass or more with respect to the composition, and the content of the nonionic surfactant being 10% by mass or more with respect to the composition. The content of the nonionic surfactant in the composition is 1.0 mass% or more with respect to the polytetrafluoroethylene. CX1X3 = CX2R (-CZ1Z2-A0) m (I) (In the formula, X1 and X3 are each independently F, Cl, H, or CF3; x2 is H, F, alkyl or fluorine-containing alkyl; a0 is an anionic group; r is a linking group; z1 and Z2 are each independently H, F, alkyl or fluorine-containing alkyl; and m is an integer of 1 or more. )

Description

[0001] This application is a divisional application. The Chinese national application number of its original application is 202080058520.1, the application date is September 7, 2020, and the invention title is "Composition and Its Manufacturing Method". Technical Field

[0002] The present invention relates to a composition containing polytetrafluoroethylene and a method for manufacturing the same. Background Art

[0003] Patent Document 1 describes a method for manufacturing an aqueous dispersion containing rod-shaped fine particles of polytetrafluoroethylene having an average aspect ratio of 2 or more, characterized in that tetrafluoroethylene is polymerized in the presence of a polymer composed of polymerization units represented by Formula 1 or a copolymer composed of polymerization units represented by Formula 1 and polymerization units represented by Formula 2 (wherein the polymerization units represented by Formula 1 are 40 mol% or more relative to all the polymerization units). In Formula 1, R f is a perfluoroalkylene group having 1 to 6 carbon atoms, M is an alkali metal ion or an ammonium ion, and in Formula 2, X is a fluorine atom or a chlorine atom.

[0004]

Chemical Formula 1

[0005]

[0006] -CF2CFX-··· Formula 2

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Laid-Open No. 11-181009 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] An object of the present invention is to provide a novel composition containing polytetrafluoroethylene and a method for manufacturing the same.

[0012] Means for Solving the Problems

[0013] According to the present invention, there is provided a composition (sometimes referred to as "the first composition" in the present invention), which is a composition containing polytetrafluoroethylene, a polymer (I) containing polymerization units (I) based on a monomer represented by the general formula (I), a nonionic surfactant, and an aqueous medium, wherein the content of the polytetrafluoroethylene in the composition is 10% by mass or more relative to the composition, and the content of the nonionic surfactant in the composition is 1.0% by mass or more relative to the polytetrafluoroethylene.

[0014] CX 1 X3 = CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0015] (In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, alkyl or fluoroalkyl; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, alkyl or fluoroalkyl; m is an integer of 1 or more.)

[0016] The stability retention time of the composition of the present invention determined by the mechanical stability test is preferably 1.0 minute or more.

[0017] The content of the above-mentioned polytetrafluoroethylene in the composition of the present invention is preferably 40% by mass or more based on the above-mentioned composition.

[0018] In the composition of the present invention, the above-mentioned nonionic surfactant is preferably represented by the general formula (i).

[0019] R 6 -O-A 1 -H (i)

[0020] (In the formula, R 6 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.)

[0021] The composition of the present invention preferably substantially does not contain a fluorosurfactant.

[0022] In the composition of the present invention, the weight average molecular weight of the polymer (I) is preferably 2.0×10 4 or more.

[0023] In the composition of the present invention, the weight average molecular weight of the polymer (I) is preferably 15.0×10 4 or more.

[0024] In the composition of the present invention, the ion exchange capacity of the polymer (I) is preferably 1.75 meg / g or more.

[0025] In the composition of the present invention, the ion exchange capacity of the polymer (I) is preferably 2.60 meg / g or more.

[0026] In the composition of the present invention, the polymer (I) is preferably water-soluble.

[0027] In the composition of the present invention, A in the general formula (I) 0 is preferably -SO3M, -COOM or -P(O)(OM)2, where in each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, and R 7 is H or an organic group).

[0028] In the composition of the present invention, the above-mentioned polytetrafluoroethylene is preferably a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units.

[0029] In the composition of the present invention, the above-mentioned modified monomer is preferably at least 1 selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group and a hydrophilic group capable of reacting in free radical polymerization.

[0030] In addition, according to the present invention, there is provided a method for manufacturing a composition, which comprises the following steps: a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the general formula (I) to obtain a polymerization dispersion containing polytetrafluoroethylene, polymer (I), and an aqueous medium; and a step of mixing the above-mentioned polymerization dispersion and a nonionic surfactant to obtain a composition containing polytetrafluoroethylene, polymer (I), a nonionic surfactant, and an aqueous medium.

[0031] CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0032] (In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, an alkyl group or a fluoroalkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluoroalkyl group; m is an integer of 1 or more.)

[0033] In the manufacturing method of the present invention, the above-mentioned nonionic surfactant is preferably represented by the general formula (i).

[0034] R 6 -O-A 1-H (i)

[0035] (In the formula, R 6 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.)

[0036] In the production method of the present invention, it is preferable to polymerize tetrafluoroethylene under conditions where a fluorosurfactant (excluding compounds having a functional group capable of reacting in radical polymerization and a hydrophilic group) is substantially absent.

[0037] In the production method of the present invention, preferably, when obtaining the above polymerization dispersion liquid, an aqueous medium and a stabilization aid are added to a reaction vessel, oxygen in the reaction vessel is removed, tetrafluoroethylene is added to the reaction vessel, and a polymerization initiator is added to the reaction vessel, thereby initiating the polymerization reaction of tetrafluoroethylene, and the above stabilization aid is removed from the polymerization dispersion liquid obtained after the end of the above polymerization reaction.

[0038] In the production method of the present invention, the weight average molecular weight of the polymer (I) is preferably 2.0×10 4 or more.

[0039] In the production method of the present invention, the weight average molecular weight of the polymer (I) is preferably 15.0×10 4 or more.

[0040] In the production method of the present invention, the ion exchange capacity of the polymer (I) is preferably 1.75 meg / g or more.

[0041] In the production method of the present invention, the ion exchange capacity of the polymer (I) is preferably 2.60 meg / g or more.

[0042] In the production method of the present invention, the polymer (I) is preferably water-soluble.

[0043] In the production method of the present invention, A in the general formula (I) 0 is preferably -SO3M, -COOM or -P(O)(OM)2 (in each formula, M is H, a metal atom, NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents or a phosphonium with or without substituents, and R 7 is H or an organic group).

[0044] The production method of the present invention preferably further includes the following step: concentrating the above composition to obtain a concentrated composition.

[0045] In the production method of the present invention, preferably, when concentrating the above composition, the above composition is heated to a temperature 5°C or more lower than the cloud point of the above nonionic surfactant, phase-separated into a supernatant phase and a concentrated phase, and the above concentrated phase is recovered, thereby obtaining a concentrated composition.

[0046] In the production method of the present invention, it is preferable to polymerize tetrafluoroethylene and a modified monomer capable of copolymerizing with tetrafluoroethylene.

[0047] In the production method of the present invention, preferably, before initiating the polymerization reaction or before the polymerization reaction proceeds and the concentration of the above polytetrafluoroethylene in the polymerization dispersion reaches 5.0% by mass, a modified monomer capable of copolymerizing with tetrafluoroethylene is added to the reaction vessel.

[0048] In the production method of the present invention, the above modified monomer is preferably at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group capable of reacting in radical polymerization and a hydrophilic group.

[0049] The production method of the present invention preferably further includes the following step: bringing the above composition into contact with an anion exchange resin or a mixed bed containing an anion exchange resin and a cation exchange resin.

[0050] In addition, according to the present invention, there is provided a composition (sometimes referred to as "the second composition" in the present invention), which is a composition containing polytetrafluoroethylene, a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), and an aqueous medium, wherein the content of the polymer (I) is 2000 mass ppm or less with respect to the above composition.

[0051] CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0052] (In the formula, X 1 and X 3 are each independently F, Cl, H, or CF3; X 2 is H, F, an alkyl group, or a fluoroalkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group, or a fluoroalkyl group; m is an integer of 1 or more.)

[0053] In the second composition of the present invention, the content of the polymer (I) is preferably 0.1 mass ppm or more relative to the above composition.

[0054] In the second composition of the present invention, the content of the above polytetrafluoroethylene is preferably 40 mass% or more relative to the above composition.

[0055] The second composition of the present invention preferably further contains an anionic hydrocarbon surfactant.

[0056] The second composition of the present invention preferably further contains a nonionic surfactant.

[0057] In the second composition of the present invention, the above nonionic surfactant is preferably represented by the general formula (i).

[0058] R 6 -O-A 1 -H (i)

[0059] (In the formula, R 6 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.)

[0060] In the second composition of the present invention, the content of the above nonionic surfactant is preferably 1.0 mass% or more relative to the above polytetrafluoroethylene.

[0061] Further, according to the present invention, there is provided a production method which is a production method of the second composition of the present invention, and which includes the following steps: a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the general formula (I), thereby obtaining a polymerization dispersion containing polytetrafluoroethylene, the polymer (I), and the aqueous medium; and a step of concentrating the above polymerization dispersion by phase separation concentration to obtain the above composition.

[0062] In the production method of the present invention, it is preferable to repeat the above phase separation concentration 2 times or more.

[0063] In addition, according to the present invention, there is provided a manufacturing method, which is a manufacturing method of the second composition of the present invention, and includes the following steps: a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the general formula (I), thereby obtaining a polymerization dispersion containing polytetrafluoroethylene, polymer (I) and an aqueous medium; a step of mixing the above polymerization dispersion and a nonionic surfactant, thereby obtaining a composition containing polytetrafluoroethylene, polymer (I), the above nonionic surfactant and an aqueous medium; and a step of heating the above composition to a temperature higher than a temperature 5 °C lower than the cloud point of the above nonionic surfactant during concentration of the above composition, phase-separating into a supernatant phase and a concentrated phase, and recovering the above concentrated phase, thereby obtaining a concentrated composition.

[0064] In the manufacturing method of the present invention, it is preferable to repeat the phase separation and concentration 2 or more times.

[0065] In addition, according to the present invention, there is provided a composition (sometimes referred to as "third composition" in the present invention), which contains polytetrafluoroethylene, a nonionic surfactant, an anionic hydrocarbon surfactant and an aqueous medium, and substantially does not contain a fluorosurfactant.

[0066] In the third composition of the present invention, the above fluorosurfactant is preferably a fluorine-containing anionic fluorosurfactant having a molecular weight of 800 or less in the anionic part.

[0067] In the third composition of the present invention, the content of the above fluorosurfactant is preferably 100 mass ppb or less.

[0068] In the third composition of the present invention, the above fluorosurfactant is preferably

[0069] F(CF2)7COOM,

[0070] F(CF2)5COOM,

[0071] H(CF2)6COOM,

[0072] CF3O(CF2)3OCHFCF2COOM,

[0073] C3F7OCF(CF3)CF2OCF(CF3)COOM,

[0074] CF3CF2CF2OCF(CF3)COOM,

[0075] CF3CF2OCF2CF2OCF2COOM,

[0076] C2F5OCF(CF3)CF2OCF(CF3)COOM,

[0077] CF3OCF(CF3)CF2OCF(CF3)COOM,

[0078] CF2ClCF2CF2OCF(CF3)CF2OCF2COOM,

[0079] CF2ClCF2CF2OCF2CF(CF3)OCF2COOM,

[0080] CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM,

[0081] CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, and

[0082]

Chemical Formula 2

[0083]

[0084] (In each formula, M is H, a metal atom, NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents) The compounds shown.

[0085] Advantages of the Invention

[0086] According to the present invention, a novel composition containing polytetrafluoroethylene and a manufacturing method thereof can be provided. Brief Description of the Drawings

[0087] Figure 1 (a) is a front view of the stirring blade used in the mechanical stability test. Figure 1 (b) is a left side view of the stirring blade used in the mechanical stability test. Detailed Description of the Invention

[0088] Hereinafter, the detailed description of the specific embodiments of the present invention will be given, but the present invention is not limited to the following embodiments.

[0089] Before specifically describing the present invention, some terms used in the present invention will be defined or explained.

[0090] In the present invention, an "organic group" refers to a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound.

[0091] Examples of this "organic group" include:

[0092] An alkyl group that may have one or more substituents,

[0093] An alkenyl group that may have one or more substituents,

[0094] An alkynyl group which may have one or more substituents,

[0095] A cycloalkyl group which may have one or more substituents,

[0096] A cycloalkenyl group which may have one or more substituents,

[0097] A cyclo-dienyl group which may have one or more substituents,

[0098] An aryl group which may have one or more substituents,

[0099] An aralkyl group which may have one or more substituents,

[0100] A non-aromatic heterocyclic group which may have one or more substituents,

[0101] A heteroaryl group which may have one or more substituents,

[0102] Cyano group,

[0103] Formyl group,

[0104] RaO-,

[0105] RaCO-,

[0106] RaSO2-,

[0107] RaCOO-,

[0108] RaNRaCO-,

[0109] RaCONRa-,

[0110] RaOCO-,

[0111] RaOSO2- and

[0112] RaNRbSO2-

[0113] (In these formulas, Ra is independently

[0114] An alkyl group which may have one or more substituents,

[0115] An alkenyl group which may have one or more substituents,

[0116] An alkynyl group which may have one or more substituents,

[0117] A cycloalkyl group which may have one or more substituents,

[0118] A cycloalkenyl group which may have one or more substituents,

[0119] A cyclo-dienyl group which may have one or more substituents,

[0120] an aryl group that may have one or more substituents,

[0121] an aralkyl group that may have one or more substituents,

[0122] a non-aromatic heterocyclic group that may have one or more substituents, or

[0123] a heteroaryl group that may have one or more substituents,

[0124] Rb is independently H or an alkyl group that may have one or more substituents).

[0125] As the above organic group, an alkyl group that may have one or more substituents is preferred.

[0126] In addition, in the present invention, the "substituent" refers to a group capable of substitution. Examples of the "substituent" include: an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heteroaryloxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heteroaryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamide group, an aromatic sulfonamide group, a heterocyclic sulfonamide group, an amino group, an aliphatic amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heteroaryloxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thio group, an aromatic thio group, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a di-aliphatic oxyphosphinyl group, and a di-aromatic oxyphosphinyl group.

[0127] The above aliphatic group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the above aliphatic group, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, can be mentioned, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc.

[0128] The above aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the above aromatic group, an aryl group having 6 to 12 carbon atoms, preferably a total of 6 to 10 carbon atoms, can be mentioned, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, a 4-methanesulfonylphenyl group, etc.

[0129] The above-mentioned heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above-mentioned heterocyclic group include a 5- or 6-membered heterocycle having 2 to 12 carbon atoms in total, preferably 2 to 10 carbon atoms, such as 2-tetrahydrofuranyl, 2-pyrimidinyl, etc.

[0130] The above-mentioned acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above-mentioned acyl group include an acyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as acetyl, propionyl, benzoyl, 3-pyridinecarbonyl, etc.

[0131] The above-mentioned acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have, for example, acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino, etc. Examples of the above-mentioned acylamino group include an acylamino group having 2 to 12 carbon atoms in total, preferably 2 to 8 carbon atoms, an alkylcarbonylamino group having 2 to 8 carbon atoms in total, such as acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino, etc.

[0132] The above-mentioned aliphatic oxycarbonyl group may be saturated or unsaturated, and may further have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above-mentioned aliphatic oxycarbonyl group include an alkoxycarbonyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, etc.

[0133] The above-mentioned carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above-mentioned carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms in total, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 5 carbon atoms in total, such as N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.

[0134] The above-mentioned aliphatic sulfonyl group may be saturated or unsaturated, and may further have a hydroxyl group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above-mentioned aliphatic sulfonyl group include an alkylsulfonyl group having 1 to 6 carbon atoms in total, preferably 1 to 4 carbon atoms in total, such as methanesulfonyl, etc.

[0135] The above-mentioned aromatic sulfonyl groups may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the above-mentioned aromatic sulfonyl groups, arylsulfonyl groups having 6 to 10 carbon atoms in total, such as benzenesulfonyl group, etc., can be mentioned.

[0136] The above-mentioned amino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc.

[0137] The above-mentioned acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. As the above-mentioned acylamino group, acylamino groups having 2 to 12 carbon atoms in total, preferably acylamino groups having 2 to 8 carbon atoms in total, and more preferably alkylcarbonylamino groups having 2 to 8 carbon atoms in total, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc., can be mentioned.

[0138] The above-mentioned aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group may be, for example, a methylsulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, etc.

[0139] The above-mentioned sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. As the above-mentioned sulfamoyl group, a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, an arylsulfamoyl group having 7 to 13 carbon atoms in total, a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total can be mentioned, and more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms in total, a dialkylsulfamoyl group having 3 to 6 carbon atoms in total, an arylsulfamoyl group having 6 to 11 carbon atoms in total, a heterocyclic sulfamoyl group having 2 to 10 carbon atoms in total, such as a sulfamoyl group, a methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, a 4-pyridinesulfamoyl group, etc.

[0140] The above-mentioned aliphatic oxy group may be saturated or unsaturated, and further may have a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. As the above-mentioned aliphatic oxy group, alkoxy groups having 1 to 8 carbon atoms in total, preferably 1 to 6 carbon atoms in total, such as a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a methoxyethoxy group, etc., can be mentioned.

[0141] The above-mentioned aromatic amino group, heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused with the aryl group, an aliphatic oxycarbonyl group, and preferably may have an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0142] The above aliphatic thio groups may be saturated or unsaturated. Additionally, alkylthio groups having a total carbon atom number of 1 to 8, more preferably 1 to 6, such as methylthio group, ethylthio group, carbamoylmethylthio group, tert-butylthio group, etc., can be cited.

[0143] The above carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. As the above carbamoylamino group, carbamoylamino group, alkylcarbamoylamino group having a total carbon atom number of 2 to 9, dialkylcarbamoylamino group having a total carbon atom number of 3 to 10, arylcarbamoylamino group having a total carbon atom number of 7 to 13, heterocyclic carbamoylamino group having a total carbon atom number of 3 to 12 can be cited. Preferably, carbamoylamino group, alkylcarbamoylamino group having a total carbon atom number of 2 to 7, dialkylcarbamoylamino group having a total carbon atom number of 3 to 6, arylcarbamoylamino group having a total carbon atom number of 7 to 11, heterocyclic carbamoylamino group having a total carbon atom number of 3 to 10, such as carbamoylamino group, methylcarbamoylamino group, N,N-dimethylcarbamoylamino group, phenylcarbamoylamino group, 4-pyridinecarbamoylamino group, etc., can be cited.

[0144] In the present invention, the range represented by the endpoints includes all the values included in this range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0145] In the present invention, the description of "at least 1" includes all the 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, etc.).

[0146] Next, the composition of the present invention and its manufacturing method will be specifically described.

[0147] The first composition of the present invention contains polytetrafluoroethylene, a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), a nonionic surfactant, and an aqueous medium. The sedimentation stability of the first composition of the present invention is excellent.

[0148] From the research by the present inventors so far, it is known that: by polymerizing tetrafluoroethylene in water using the polymer (I), a composition containing polytetrafluoroethylene and an aqueous medium can be stably and efficiently manufactured. Additionally, it is also known that: by polymerizing tetrafluoroethylene in an aqueous medium using the polymer (I), high molecular weight polytetrafluoroethylene can be obtained in a high yield.

[0149] The present invention relates to technologies discovered based on these technical ideas, and further relates to technologies for improving the sedimentation stability of a composition containing polytetrafluoroethylene after production. According to new research findings of the present inventors, by using polymer (I) and a nonionic surfactant, the sedimentation stability of a composition containing polytetrafluoroethylene and an aqueous medium is surprisingly improved.

[0150] That is, since the first composition of the present invention contains polymer (I) and a nonionic surfactant, polytetrafluoroethylene dispersed in the aqueous medium is difficult to settle. Therefore, even when the concentration of polytetrafluoroethylene in the composition increases, the viscosity of the composition is difficult to increase, and thus the processability of the composition of the present invention is excellent. In addition, even when the composition contains a relatively large amount of polytetrafluoroethylene, the composition exhibits excellent sedimentation stability. Therefore, by using the composition of the present invention, products such as coating films, impregnated bodies, and casting films can be manufactured with high efficiency, and it is also difficult to occur molding defects during product manufacturing caused by aggregates of polytetrafluoroethylene.

[0151] For the first composition of the present invention, the stability retention time measured by a mechanical stability test of the composition is preferably 1.0 minute or more. As the stability retention time, in order of preference, it is 2.0 minutes or more, 5.0 minutes or more, 10.0 minutes or more, 15.0 minutes or more, 20.0 minutes or more, 30.0 minutes or more, 40.0 minutes or more, 50.0 minutes or more, 60.0 minutes or more. In addition, as the stability retention time, in order of preference, it is 180.0 minutes or less, 120.0 minutes or less. When the composition of the present invention exhibits a stability retention time within the above range, polytetrafluoroethylene in the composition is difficult to settle, and in addition, the viscosity of the composition is difficult to increase. Therefore, the composition exhibiting a stability retention time within the above range has excellent processability, can manufacture products such as coating films, impregnated bodies, and casting films with high efficiency, and it is also difficult to occur molding defects during product manufacturing.

[0152] The second composition of the present invention contains polytetrafluoroethylene, polymer (I) containing a polymerization unit (I) based on a monomer represented by the general formula (I), and an aqueous medium, and the content of polymer (I) is 2000 mass ppm or less relative to the composition. Since the content of polymer (I) in the second composition of the present invention is small, by using the second composition of the present invention, the excellent properties possessed by polytetrafluoroethylene are fully exerted.

[0153] According to the research of the present inventors so far, by using polymer (I) to polymerize tetrafluoroethylene in water, a composition containing polytetrafluoroethylene and an aqueous medium can be stably and efficiently manufactured. In addition, it is also known that by using polymer (I) to polymerize tetrafluoroethylene in an aqueous medium, polytetrafluoroethylene with a high molecular weight can be obtained in a high yield.

[0154] The present invention relates to technologies discovered based on these technical ideas, and further relates to technologies for reducing the content of polymer (I) in a composition containing polytetrafluoroethylene after production. According to new research findings of the present inventors, by using a new method, the content of polymer (I) in the composition can be surprisingly reduced.

[0155] That is, since the content of polymer (I) in the second composition of the present invention is 2000 mass ppm or less, when products such as coating films, impregnated bodies, and casting films are manufactured using the second composition of the present invention, products that hardly contain polymer (I) and fully exhibit the excellent properties possessed by polytetrafluoroethylene can be obtained.

[0156] The second composition of the present invention preferably further contains a nonionic surfactant. By containing a nonionic surfactant, the sedimentation stability of the composition can be improved. The second composition of the present invention preferably exhibits the same stability retention time as the first composition of the present invention.

[0157] The second composition of the present invention preferably further contains an anionic hydrocarbon surfactant. By containing an anionic hydrocarbon surfactant, the sedimentation stability of the composition can be improved.

[0158] The third composition of the present invention contains polytetrafluoroethylene, a nonionic surfactant, an anionic hydrocarbon surfactant, and an aqueous medium, and substantially does not contain a fluorosurfactant.

[0159] There is a need for a composition with excellent sedimentation stability, and this composition substantially does not contain a fluorosurfactant. Although the third composition of the present invention substantially does not contain a fluorosurfactant, since it contains a nonionic surfactant and an anionic hydrocarbon surfactant, the polytetrafluoroethylene dispersed in the aqueous medium is also difficult to settle. Therefore, even when the concentration of polytetrafluoroethylene in the composition increases, the viscosity of the composition is difficult to increase, and thus the processability of the composition of the present invention is excellent. In addition, even when the composition contains a relatively large amount of polytetrafluoroethylene, the composition exhibits excellent sedimentation stability. Therefore, by using the composition of the present invention, products such as coating films, impregnated bodies, and casting films can be manufactured with high efficiency.

[0160] The third composition of the present invention preferably further contains a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I). By containing the polymer (I), the sedimentation stability of the composition can be improved. The third composition of the present invention preferably exhibits the same stability retention time as the first composition of the present invention.

[0161] Next, the compositions of the first composition, the second composition, and the third composition of the present invention will be described in more detail.

[0162] <Polytetrafluoroethylene>

[0163] Polytetrafluoroethylene (PTFE) generally has stretchability, fibrillating properties, and non-melting secondary processability. Non-melting secondary processability refers to the property that the melt flow rate cannot be measured at temperatures above the crystallization melting point according to ASTM D 1238 and D 2116, that is, the property of not being easily flowable in the melting temperature range.

[0164] PTFE can be a tetrafluoroethylene (TFE) homopolymer or a modified PTFE containing TFE units and modified monomer units.

[0165] As the modified monomer, as long as it can copolymerize with TFE, there is no particular limitation, and fluorinated monomers and non-fluorinated monomers can be cited.

[0166] As the non-fluorinated monomer, there is no particular limitation, and the general formula can be cited:

[0167] CH2=CR Q1 -LR Q2

[0168] (In the formula, R Q1 represents a hydrogen atom or an alkyl group. L represents a single bond, -CO-O-*, -O-CO-*, or -O-. * represents the bonding position with R Q2 . R Q2 represents a hydrogen atom, an alkyl group, or a nitrile group) of the monomer shown.

[0169] As the non-fluorinated monomer, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, vinyl methacrylate, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, ethyl vinyl ether, cyclohexyl vinyl ether, etc. can be cited. As the non-fluorinated monomer, butyl methacrylate, vinyl acetate, and acrylic acid are preferred among them.

[0170] As the fluorinated monomer, for example, perfluoroolefins such as hexafluoropropylene [HFP]; fluorochloroolefins such as chlorotrifluoroethylene [CTFE]; hydrogen-containing fluorinated olefins such as trifluoroethylene, vinylidene fluoride [VDF]; fluoro(alkyl vinyl ether); (perfluoroalkyl)ethylene; perfluoroallyl ether, etc. can be cited.

[0171] In addition, the modified monomer used can be one kind or two or more kinds.

[0172] As the fluoro(alkyl vinyl ether), there is no particular limitation, and for example, the general formula (A) can be cited:

[0173] CF2=CF-ORf (A)

[0174] (In the formula, Rf represents a perfluoro organic group) and other perfluoro unsaturated compounds. In the present invention, the above-mentioned "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The above-mentioned perfluoro organic group may have an ether oxygen atom.

[0175] As the fluoro(alkyl vinyl ether), for example, perfluoro(alkyl vinyl ether) (PAVE) in which Rf in the general formula (A) is a perfluoroalkyl group having 1 to 10 carbon atoms can be cited. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

[0176] As the perfluoroalkyl group in PAVE, for example, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, etc. can be cited.

[0177] As the fluoro(alkyl vinyl ether), further, a monomer in which Rf in the general formula (A) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, a monomer in which Rf is the following formula:

[0178]

Chemical formula 3

[0179]

[0180] (In the formula, m represents an integer of 0 or 1 to 4), a monomer in which Rf is the following formula:

[0181] CF3CF2CF2-(O-CF(CF3)-CF2) n -

[0182] (In the formula, n represents an integer of 1 to 4), and other monomers.

[0183] As the hydrogen-containing fluoroolefin, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E isomer), CHF=CHCF3 (Z isomer), etc. can be cited.

[0184] As the fluoro(alkyl vinyl ether), it is preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE), and more preferably PMVE.

[0185] As the (perfluoroalkyl)ethylene (PFAE), there is no particular limitation, and for example, (perfluorobutyl)ethylene (PFBE), (perfluorohexyl)ethylene, (perfluorooctyl)ethylene, etc. can be cited.

[0186] As the perfluoroallyl ether, for example

[0187] General formula: CF2=CF-CF2-ORf

[0188] A fluorine-containing monomer represented by (wherein, Rf represents a perfluoro organic group).

[0189] Rf in the above general formula is the same as Rf in general formula (A). As Rf, a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms is preferred. As the perfluoroallyl ether, at least one selected from the group consisting of CF2=CF-CF2-O-CF3, CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is preferred, more preferably at least one selected from the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9, and further preferably CF2=CF-CF2-O-CF2CF2CF3.

[0190] In the modified PTFE, the content of the modified monomer unit is preferably in the range of 0.00001% by mass to 1.0% by mass with respect to all the polymerization units. As the lower limit, 0.0001% by mass is preferred, 0.001% by mass is more preferred, and 0.005% by mass is further preferred. As the upper limit of the content of the modified monomer unit, in order of preference, they are 0.90% by mass, 0.50% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, and 0.05% by mass. In the present invention, the above-mentioned modified monomer unit refers to the part derived from the modified monomer that is a part of the molecular structure of the modified PTFE.

[0191] As the modified monomer, a comonomer (3) having a monomer reactivity ratio of 0.1 to 8 is also preferably exemplified. By the presence of the comonomer (3), PTFE particles having a small particle size can be obtained, and a composition having excellent sedimentation stability can be obtained.

[0192] Here, the monomer reactivity ratio in the copolymerization with TFE is a value obtained as follows: when the growing radical is less than the repeating unit based on TFE, the value obtained by dividing the rate constant when the growing radical reacts with TFE by the rate constant when the growing radical reacts with the comonomer is the above-mentioned monomer reactivity ratio. The lower this value, the higher the reactivity of the comonomer with TFE. The monomer reactivity ratio can be calculated as follows: copolymerize TFE and the comonomer, determine the composition in the resulting polymer at the beginning, and calculate it from the Fineman-Ross equation.

[0193] The above copolymerization was carried out in a stainless-steel autoclave with an internal volume of 6.0 L using 3600 g of deionized and degassed water, 1000 mass ppm of ammonium perfluorooctanoate relative to the above water, and 100 g of paraffin at a pressure of 0.78 MPa and a temperature of 70 °C. 0.05 g, 0.1 g, 0.2 g, 0.5 g, and 1.0 g of the comonomer were respectively added to the reactor, and 0.072 g of ammonium persulfate (20 mass ppm relative to water) was added. To maintain a polymerization pressure of 0.78 MPa, TFE was continuously supplied. When the TFE feed amount reached 1000 g, stirring was stopped and the pressure was released until the reactor reached atmospheric pressure. After cooling, the paraffin was separated, and an aqueous dispersion containing the produced polymer was thus obtained. The above aqueous dispersion was stirred to precipitate the produced polymer, and dried at 150 °C. The composition in the obtained produced polymer was calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis according to the type of monomer.

[0194] As the comonomer (3) with a monomer reactivity ratio of 0.1 to 8, at least one selected from the group consisting of the comonomers represented by formulas (3a) to (3d) is preferred.

[0195] CH2=CH-Rf 1 (3a)

[0196] (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms.)

[0197] CF2=CF-O-Rf 2 (3b)

[0198] (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 2 carbon atoms.)

[0199] CF2=CF-O-(CF2) n CF=CF2 (3c)

[0200] (In the formula, n is 1 or 2.)

[0201]

Chemical Formula 4

[0202]

[0203] (In the formula, X 3 and X 4 are F, Cl, or methoxy, and Y is formula Y1 or Y2.)

[0204]

Chemical Formula 5

[0205] -CF=CF- (Y1)

[0206]

[0207] (In formula Y2, Z and Z' are F or fluoroalkyl groups having 1 to 3 carbon atoms.)

[0208] The content of the copolymer monomer (3) unit is preferably in the range of 0.00001% by mass to 1.0% by mass with respect to all the polymer units of the modified PTFE. As the lower limit, it is more preferably 0.0001% by mass, further preferably 0.001% by mass, still further preferably 0.005% by mass, and particularly preferably 0.009% by mass. As the upper limit, in order of preference, they are 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, 0.08% by mass, 0.05% by mass, and 0.01% by mass.

[0209] As the above-mentioned modified monomer, since a composition having a small average primary particle diameter of the modified polytetrafluoroethylene particles, a small aspect ratio of the primary particles, and excellent sedimentation stability can be obtained, it is preferably at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group and a hydrophilic group capable of reacting in radical polymerization. By using the above-mentioned modified monomer, a composition having a smaller average primary particle diameter, a small aspect ratio of the primary particles, and excellent sedimentation stability can be obtained. In addition, a composition with less precipitated polymer can be obtained.

[0210] The modified monomer also preferably contains a modified monomer having a functional group and a hydrophilic group capable of reacting in radical polymerization (hereinafter referred to as "modified monomer (A)").

[0211] By the presence of the modified monomer (A), PTFE particles having a small primary particle diameter can be obtained, and a composition having excellent sedimentation stability can be obtained. In addition, the amount of the non-precipitated polymer can be reduced. Furthermore, the aspect ratio of the primary particles can be reduced.

[0212] PTFE containing TFE units and modified monomer (A) units can be obtained, for example, by polymerizing TFE and modified monomer (A) in an aqueous medium. The amount of the modified monomer (A) used during polymerization is preferably an amount exceeding the amount corresponding to 0.1 mass ppm of the aqueous medium, more preferably an amount exceeding 0.5 mass ppm, further preferably an amount exceeding 1.0 mass ppm, still further preferably 5 mass ppm or more, and particularly preferably 10 mass ppm or more. If the amount of the modified monomer (A) used is too small, the average primary particle diameter of the obtained PTFE may not be reduced. The amount of the modified monomer (A) used may be in the above range. For example, the upper limit can be 5000 mass ppm.

[0213] The modified monomer (A) has high water solubility. Therefore, even when the composition contains unreacted modified monomer (A), the modified monomer (A) can be easily removed from the composition by methods such as concentration, precipitation, washing, etc.

[0214] Examples of the hydrophilic group in the modified monomer (A) include, for example, -NH2, -PO3M, -P(O)(OM)2, -OPO3M, -OP(O)(OM)2, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, and R 7 is H or an organic group, which may be the same or different. Any two of them may bond to each other to form a ring). Among the above hydrophilic groups, -SO3M or -COOM is preferred.

[0215] As the organic group of R 7 is preferably an alkyl group.

[0216] As R 7 , preferably H or an organic group of C 1-10 , more preferably H or an organic group of C 1-4 , further preferably H or an alkyl group of C 1-4 .

[0217] Examples of the above metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1), alkaline earth metals (Group 2), etc., and preferably Na, K, or Li.

[0218] Examples of the "functional group capable of reacting in free radical polymerization" in the modified monomer (A) include groups having an ethylenic unsaturated bond such as vinyl and allyl. The group having an ethylenic unsaturated bond can be represented by the following formula:

[0219] CX e X g =CX f R-

[0220] (In the formula, X e , X f and X g are each independently F, Cl, H, CF3, CF2H, CFH2, or CH3; and R is a linking group). Examples of the linking group of R include the linking group of R a described later. Preferably, -CH=CH2, -CF=CH 2、 -CH=CF 2、Groups having unsaturated bonds such as -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CH=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, and -O-CF2-CF=CF2.

[0221] Since the modified monomer (A) has a functional group that can react in free radical polymerization, it is presumed that if used in polymerization, it will react with TFE in the early stage of the polymerization reaction to form particles having a hydrophilic group derived from the modified monomer (A) and high stability. Therefore, it is believed that if polymerization is carried out in the presence of the modified monomer (A), the number of particles will increase.

[0222] During the polymerization, the above-mentioned modifying monomer (A) may be present alone or in combination of two or more.

[0223] In the polymerization, a compound having an unsaturated bond can be used as the modifying monomer (A).

[0224] The modified monomer (A) is preferably of the general formula (4A):

[0225] CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4A)

[0226] (Where X i , X j and X k Each independently represents F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a connecting group; Z 1 and Z 2 Each independently represents H, F or CF3, and k represents 0 or 1).

[0227] Examples of the hydrophilic group include -NH2, -PO3M, -P(O)(OM)2, -OPO3M, -OP(O)(OM)2, -SO3M, -OSO3M, -COOM (wherein M is H, a metal atom, NR 74. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7 is H or an organic group, which may be the same or different. Any two of them can be bonded to each other to form a ring). As the above hydrophilic group, -SO3M or -COOM is preferred. As R 7 , H or C 1-10 is preferred for the organic group, more preferably H or C 1-4 is preferred for the organic group, and even more preferably H or C 1-4 is the alkyl group.

[0228] As the above metal atom, monovalent and divalent metal atoms can be mentioned, such as alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.

[0229] By using the modified monomer (4A), a composition with a smaller average primary particle size and more excellent sedimentation stability can be obtained. In addition, the aspect ratio of the primary particles can be further reduced.

[0230] The above R a is a linking group. In the present invention, the "linking group" refers to a divalent linking group. The linking group can be a single bond, preferably contains at least 1 carbon atom, and the number of carbon atoms can be 2 or more, can be 4 or more, can be 8 or more, can be 10 or more, and can also be 20 or more. There is no limit to the upper limit, for example, it can be 100 or less, or can be 50 or less.

[0231] The above linking group can be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and can contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen as desired, and can contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, carbamate, urea, and urethane as desired. The above linking group does not contain carbon atoms and can be a linear heteroatom such as oxygen, sulfur, or nitrogen.

[0232] The above R a is preferably a linear heteroatom such as oxygen, sulfur, nitrogen, or a divalent organic group.

[0233] R a When it is a divalent organic group, the hydrogen atom bonded to the carbon atom can be substituted by a halogen other than fluorine, such as chlorine, etc., and can contain or not contain a double bond. In addition, R a can be either linear or branched, and can be either cyclic or acyclic. In addition, R a can contain functional groups (such as ester, ether, ketone, amine, halide, etc.).

[0234] In addition, R aIt can be a divalent organic group that is non-fluorinated, or a partially fluorinated or perfluorinated divalent organic group.

[0235] As R a , it can be, for example: a hydrocarbon group in which no fluorine atom is bonded to a carbon atom; a hydrocarbon group in which a part of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms; a hydrocarbon group in which all of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms; a hydrocarbon group containing -(C=O)-, -(C=O)-O- or -(C=O)-, which may contain an oxygen atom, a double bond, or a functional group.

[0236] R a Preferably, it is a hydrocarbon group having 1 to 100 carbon atoms that contains or does not contain -(C=O)-, -(C=O)-O- or an ether bond, and contains or does not contain a carbonyl group, and in this hydrocarbon group, a part or all of the hydrogen atoms bonded to a carbon atom may be replaced by fluorine.

[0237] As R a , preferably selected from -(CH2) a -, -(CF2) a -, -O-(CF2) a -, -(CF2) a -O-(CF2) b -, -O(CF2) a -O-(CF2) b -, -(CF2) a -[O-(CF2) b c -, -O(CF2) a -[O-(CF2) b c -, -[(CF2) a -O] b -[(CF2) c -O] d -, -O[(CF2) a -O] b -[(CF2) c -O] d -, -O-[CF2CF(CF3)O] a -(CF2) b -, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2) a -, -(C=O)-(CF2) a -, -(C=O)-O-(CH2) a -, -(C=O)-O-(CF2) a -, -(C=O)-[(CH2) a -O] b ​​-, -(C=O)-[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -, -(C=O)-O[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -(CH2) c -, -(C=O)-O[(CF2) a -O] b -(CF2) c -, -(C=O)-(CH2) a -O-(CH2) b -, -(C=O)-(CF2) a -O-(CF2) b -, -(C=O)-O-(CH2) a -O-(CH2) b -, -(C=O)-O-(CF2) a -O-(CF2) b -, -(C=O)-O-C6H4-, and at least one of their combinations.

[0238] In the formula, a, b, c, and d are independently at least 1 or more. a, b, c, and d can independently be 2 or more, can be 3 or more, can be 4 or more, can be 10 or more, and can also be 20 or more. The upper limit of a, b, c, and d is, for example, 100.

[0239] As R a Preferred specific examples include -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CH2-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -, -(C=O)-[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n-, -(C=O)-O[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-(CH2)2-O-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-, -(C=O)-O-C6H4-, etc. Among them, specifically, the above R a Preferably -CF2-O-, -CF2-O-CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-O-(CH2)-, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-(CH2)2-O-(CH2)-, or -(C=O)-O-C6H4-.

[0240] In the above formula, n is an integer from 1 to 10.

[0241] As -R in the general formula (4A) a -(CZ 1 Z 2 ) k-, preferably -CF2-O-CF2-, -CF2-O-CF(CF3)-, -CF2-O-C(CF3)2-, -CF2-O-CF2-CF2-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2-C(CF3)2-, -CF2-O-CF2CF2-CF2-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF2CF2-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)CF2-CF2-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-C(CF3)2-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-C(CF3)2-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -(CH2)-, -(C=O)-[(CF2)2-O] n -(CF2)-, -(C=O)-[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-[(CF2)2-O] n -(CF2)-(CF2)-, -(C=O)-O[(CH2)2-O] n -(CF2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-O[(CF2)2-O] n-(CF2)-(CF2)-, -(C=O)-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, -(C=O)-O-(CF2)2-O-(CF2)-C(CF3)2-, or -(C=O)-O-C6H4-C(CF3)2-, more preferably -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -(C=O)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CH2)-(CH2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, or -(C=O)-O-C6H4-C(CF3)2-.

[0242] In the above formula, n is an integer from 1 to 10.

[0243] As a specific example of the compound represented by the general formula (4A), there can be cited

[0244]

Chemical Formula 6

[0245]

[0246] (In the formula, X j and Y 3 are the same as above. n is an integer from 1 to 10) etc.

[0247] As R a , preferably the general formula (r1):

[0248] -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g - (r1)

[0249] (In the formula, X 6Each independently represents H, F or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1), and the divalent group shown is also preferably the general formula (r2):

[0250] -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g - (r2)

[0251] (In the formula, X 7 Each independently represents H, F or CF3, e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1), and the divalent group shown.)

[0252] As -R in the general formula (4A) a -(CZ 1 Z 2 ) k -, is also preferably the general formula (t1):

[0253] -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 - (t1)

[0254] (In the formula, X 6 Each independently represents H, F or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, Z 1 and Z 2 Each independently represents F or CF3), in the formula (t1), Z 1 and Z 2 More preferably, one is F and the other is CF3.)

[0255] In addition, in the general formula (4A), as -R a -(CZ 1 Z 2 ) k -, is also preferably the general formula (t2):

[0256] -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g -CZ1 Z 2 - (t2)

[0257] (wherein X 7 are each independently H, F or CF3, e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, Z 1 and Z 2 are each independently a divalent group represented by F or CF3), in formula (t2), Z 1 and Z 2 more preferably, one is F and the other is CF3.

[0258] The compound represented by general formula (4A) is also preferably a compound having a C-F bond and no C-H bond except for the hydrophilic group (Y 3 ). That is, in general formula (4A), it is preferred that X i , X j and X k are all F, R a is a perfluoroalkylene group having 1 or more carbon atoms. The above perfluoroalkylene group can be either linear or branched, can be either cyclic or acyclic, and can contain at least 1 chain-like heteroatom. The number of carbon atoms of the above perfluoroalkylene group can be 2 to 20, or can be 4 to 18.

[0259] The compound represented by general formula (4A) can also be partially fluorinated. That is, the compound represented by general formula (4A) is also preferably a compound having at least 1 hydrogen atom bonded to a carbon atom and at least 1 fluorine atom bonded to a carbon atom except for the hydrophilic group (Y 3 ).

[0260] The compound represented by general formula (4A) is also preferably a compound represented by the following formula (4A-a).

[0261] CF2=CF-O-Rf 0 -Y 3 (4A-a)

[0262] (wherein Y 3 is a hydrophilic group, Rf 0 is perfluorinated, can be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and is a perfluorinated divalent linking group optionally additionally containing 1 or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen).

[0263] The compound represented by general formula (4A) is also preferably a compound represented by the following formula (4A-b).

[0264] CH2=CH-O-Rf 0 -Y 3 (4A-b)

[0265] (In the formula, Y 3 is a hydrophilic group, and Rf 0 is a perfluorinated divalent linking group defined by formula (4A-a).)

[0266] In general formula (4A), Y 3 being -OSO3M is one of the preferred modes. When Y 3 is -OSO3M, examples of the compound represented by general formula (4A) include CF2=CF(OCF2CF2CH2OSO3M), CH2=CH((CF2)4CH2OSO3M), CF2=CF(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF(CF3)CH2OSO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M), CH2=CH((CF2)4CH2OSO3M), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), etc. In the above formulas, M is the same as described above.

[0267] In general formula (4A), Y 3 being -SO3M is also one of the preferred modes. When Y 3 is -SO3M, examples of the polymerization unit based on the compound represented by general formula (4A) include CF2=CF(OCF2CF2SO3M), CF2=CF(O(CF2)4SO3M), CF2=CF(OCF2CF(CF3)SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M), CH2=CH(CF2CF2SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M), CH2=CH((CF2)4SO3M), CH2=CH(CF2CF2SO3M), CH2=CH((CF2)3SO3M), etc. In the above formulas, M is the same as described above.

[0268] In general formula (4A), Y 3 being -COOM is also one of the preferred modes. When Y 3In the case of -COOM, as the compound represented by the general formula (4A), examples include CF2=CF(OCF2CF2COOM), CF2=CF(OCF2CF2CF2COOM), CF2=CF(O(CF2)5COOM), CF2=CF(OCF2CF(CF3)COOM), CF2=CF(OCF2CF(CF3)O(CF2) n COOM) (n>1), CH2=CH(CF2CF2COOM), CH2=CH((CF2)4COOM), CH2=CH(CF2CF2COOM), CH2=CH((CF2)3COOM), CF2=CF(OCF2CF2SO2NR’CH2COOM), CF2=CF(O(CF2)4SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM), CH2=CH(CF2CF2SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM), CH2=CH((CF2)4SO2NR’CH2COOM), CH2=CH(CF2CF2SO2NR’CH2COOM), CH2=CH((CF2)3SO2NR’CH2COOM), etc. In the above formula, R’ is H or C 1-4 alkyl group, and M is the same as above.

[0269] In the general formula (4A), Y 3 being -OPO3M or -OP(O)(OM)2 is also one of the preferred modes. Y 3In the case of -OPO3M or -OP(O)(OM)2, examples of the compound represented by the general formula (4A) include CF2=CF(OCF2CF2CH2OP(O)(OM)2), CF2=CF(O(CF2)4CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CH2=CH(CF2CF2CH2OP(O)(OM)2, CH2=CH((CF2)4CH2OP(O)(OM)2), CH2=CH(CF2CF2CH2OP(O)(OM)2), CH2=CH((CF2)3CH2OP(O)(OM)2), etc. In the above formula, M is the same as described above.

[0270] In the general formula (4A), Y 3 being -PO3M or -P(O)(OM)2 is also one of the preferred modes. Y 3 In the case of -PO3M or -OP(O)(OM)2, examples of the compound represented by the general formula (4A) include CF2=CF(OCF2CF2P(O)(OM)2), CF2=CF(O(CF2)4P(O)(OM)2), CF2=CF(OCF2CF(CF3)P(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2), CH2=CH(CF2CF2P(O)(OM)2), CH2=CH((CF2)4P(O)(OM)2), CH2=CH(CF2CF2P(O)(OM)2), CH2=CH((CF2)3P(O)(OM)2), etc., where M is the same as described above.

[0271] The compound represented by the general formula (4A) is preferably at least one selected from the group consisting of the following compounds, which are of the general formula (5A):

[0272] CX2=CY(-CZ2-O-Rf-Y 3 )(5A)

[0273] (In the formula, Xs are the same or different and are -H or -F, Y is -H, -F, an alkyl group or a fluoroalkyl group, and Zs are the same or different and are -H, -F, an alkyl group or a fluoroalkyl group. Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having 2 to 100 carbon atoms and having an ether bond. Y 3 is the same as described above).) The compound represented by the general formula (6A):

[0274] CX2=CY(-O-Rf-Y 3 ) (6A)

[0275] (In the formula, Xs are the same or different and are -H or -F, Y is -H, -F, an alkyl group or a fluoroalkyl group, and Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having 2 to 100 carbon atoms and having an ether bond. Y 3 is the same as described above).) The compound represented by the general formula (7A):

[0276] CX2=CY(-Rf-Y 3 ) (7A)

[0277] (In the formula, Xs are the same or different and are -H or -F, Y is -H, -F, an alkyl group or a fluoroalkyl group, and Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having 2 to 100 carbon atoms and having an ether bond. Y 3 is the same as described above).) The compound represented by the general formula (5A) is as follows.

[0278] In the general formula (5A), X is -H or -F. Both Xs can be -F, or at least one of them can be -H. For example, one can be -F and the other can be -H, or both can be -H.

[0279] In the general formula (5A), Y is -H, -F, an alkyl group or a fluoroalkyl group. The above alkyl group is an alkyl group without fluorine atoms and can have 1 or more carbon atoms. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above fluoroalkyl group is an alkyl group containing at least 1 fluorine atom and can have 1 or more carbon atoms. The number of carbon atoms of the above fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. As the above Y, -H, -F or -CF3 is preferred, and -F is more preferred.

[0280] In general formula (5A), Zs, which may be the same or different, are -H, -F, an alkyl group, or a fluoroalkyl group. The above-mentioned alkyl group is an alkyl group that does not contain a fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above-mentioned alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above-mentioned fluoroalkyl group is an alkyl group that contains at least 1 fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above-mentioned fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As the above-mentioned Z, -H, -F, or -CF3 is preferred, and -F is more preferred.

[0281] In general formula (5A), at least one of the above-mentioned X, Y, and Z preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0282] In general formula (5A), the above-mentioned Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having an ether bond and 2 to 100 carbon atoms. The number of carbon atoms of the above-mentioned fluoroalkylene group is preferably 2 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less. Examples of the above-mentioned fluoroalkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The above-mentioned fluoroalkylene group is preferably a perfluoroalkylene group.

[0283] The number of carbon atoms of the fluoroalkylene group having an ether bond is preferably 3 or more. In addition, the number of carbon atoms of the fluoroalkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and still more preferably 12 or less. As the fluoroalkylene group having an ether bond, for example, the following formula is also preferred:

[0284] [Chemical formula 7]

[0285]

[0286] (In the formula, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F, or CF3; p1 + q1 + r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5) represents a divalent group.

[0287] As the above-mentioned fluoroalkylene group having an ether bond, specifically, -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)-(where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O)n -CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorinated alkylene group having an ether bond is preferably a perfluoroalkylene group.)

[0288] In the general formula (5A), Y 3 is preferably -COOM, -SO3M or -OSO3M (where M is H, a metal atom, NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 7 is H or an organic group, which may be the same or different. Any two of them can be bonded to each other to form a ring). As the organic group in R 7 , an alkyl group is preferred. As R 7 , H or a C 1-10 organic group is preferred, more preferably H or a C 1-4 organic group, and further preferably H or a C 1-4 alkyl group. As the above metal atom, alkali metals (Group 1), alkaline earth metals (Group 2), etc. can be mentioned, and Na, K or Li is preferred. As the above 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, further preferably -H, -Na, -K, -Li or -NH4, still more preferably -Na, -K or -NH4, particularly preferably -Na or -NH4, and most preferably -NH4. As the above Y 3 , -COOM or -SO3M is preferred, and -COOM is more preferred.)

[0289] The compound represented by the general formula (5A) is preferably the compound (5a) represented by the general formula (5a).

[0290] CH2=CF(-CF2-O-Rf-Y 3 ) (5a)

[0291] (wherein, Rf and Y 3 are the same as above.)

[0292] As the compound represented by the general formula (5b), specifically, the following formula can be cited:

[0293]

Chemical Formula 8

[0294]

[0295] (wherein, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; p1 + q1 + r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, and Y 3 is the same as above. Among them, when both Z 3 and Z 4 are H, p1 + q1 + r1 + s1 is not 0) compounds represented by. More specifically, preferably, there can be cited

[0296]

Chemical Formula 9

[0297]

[0298] CH2 = CFCF2OCH2CF2 - Y 3 , CH2 = CFCF2O(CH2CF2CF20)CH2CF2 - Y 3 ,

[0299] CH2 = CFCF2OCH2CF2CH2 - Y 3 ,

[0300] CH2 = CFCF2O(CH2CF2CF2O)CH2CF2CH2 - Y 3 ,

[0301] CH2 = CFCF2OCF2CF2 - Y 3 , CH2 = CFCF2O(CF2CF2CF2O)CF2CF2 - Y 3 ,

[0302] CH2 = CFCF2OCF2CF2CH2 - Y 3 .

[0303] CH2 = CFCF2O(CF2CF2CF2O)CF2CF2CH2 - Y 3 ,

[0304] CH2 = CFCF2OCF2 - Y 3 , CH2 = CFCF2O(CF2Cf2O)CF2 - Y 3 ,

[0305] CH2 = CFCF2OCF2CH2 - Y 3 ,

[0306] CH2 = CFCF2O(CF2CF2O)CF2CH2 - Y 3 , etc., among which the preferred ones are

[0307]

Chemical 10

[0308]

[0309] As the compound represented by the general formula (5a), Y in the formula (5a) is preferably 3 -COOM, and at least one selected from the group consisting of CH2═CFCF2OCF(CF3)COOM and CH2═CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is as defined above) is particularly preferred, and CH2═CFCF2OCF(CF3)COOM is more preferred.

[0310] The compound represented by the general formula (5A) is preferably the compound (5b) represented by the general formula (5b).

[0311] CX 2 2═CFCF2 - O - (CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5b)

[0312] (wherein each X 2 is the same and represents F or H. n5 represents an integer of 0 or 1 to 10, and Y 3 is as defined above.)

[0313] In the general formula (5b), from the viewpoint of the sedimentation stability of the obtained composition, n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1 or 2, and further preferably 0 or 1. From the viewpoints of obtaining appropriate water solubility and the sedimentation stability of the composition, Y 3 is preferably -COOM; from the viewpoints of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M is preferably H or NH4.

[0314] Examples of the compound represented by the general formula (5c) include CH2═CFCF2OCF(CF3)COOM and CH2═CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is as defined above).

[0315] In addition, examples of the compound represented by the general formula (5A) also include the compound represented by the general formula (5c) and the like.

[0316] CF2═CFCF2 - O - Rf - Y 3 (5c)

[0317] (wherein Rf and Y 3 are the same as above.)

[0318] More specifically, examples include

[0319] [Chemical 11]

[0320] CF2=CFCF2OCF2CF2CF2-Y 3 ,

[0321]

[0322] CF2=CFCF2OCF2CF2CF2CH2-Y 3 ,

[0323] etc.

[0324] In general formula (6A), X is -H or -F. Both X can be -F, or at least one of them can be -H. For example, one can be -F and the other can be -H, or both can be -H.

[0325] In general formula (6A), Y is -H, -F, an alkyl group, or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain fluorine atoms, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above fluoroalkyl group is an alkyl group that contains at least 1 fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. As the above Y, -H, -F, or -CF3 is preferred, and -F is more preferred.

[0326] In general formula (6A), at least one of the above X and Y preferably contains a fluorine atom. For example, X can be -H, and Y and Z can be -F.

[0327] In general formula (6A), the above Rf is a fluoroalkylene group having 1 to 40 carbon atoms, or a fluoroalkylene group having an ether bond and 2 to 100 carbon atoms. The number of carbon atoms of the above fluoroalkylene group is preferably 2 or more. In addition, the number of carbon atoms of the above fluoroalkylene group is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less. Examples of the above fluoroalkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The above fluoroalkylene group is preferably a perfluoroalkylene group.

[0328] In the above general formula (6A), Y 3 is preferably -COOM, -SO3M, or -OSO3M (M is H, a metal atom, NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 7is H or an organic group, which may be the same or different. Any two of them may bond to each other to form a ring).

[0329] As R 7 the organic group is preferably an alkyl group. As R 7 , preferably H or C 1-10 the organic group, more preferably H or C 1-4 the organic group, further preferably H or C 1-4 the alkyl group.

[0330] As the above-mentioned metal atom, alkali metals (Group 1), alkaline earth metals (Group 2), etc. can be cited, and Na, K or Li is preferred.

[0331] As the above-mentioned 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, further preferably -H, -Na, -K, -Li or -NH4, still more preferably -Na, -K or -NH4, particularly preferably -Na or -NH4, and most preferably -NH4.

[0332] As the above-mentioned Y 3 , preferably -COOM or -SO3M, more preferably -COOM.

[0333] The compound represented by the general formula (6A) is preferably at least one selected from the group consisting of the compounds represented by the general formulas (6a), (6b), (6c), (6d) and (6e).

[0334] CF2=CF-O-(CF2) n1 -Y 3 (6a)

[0335] (In the formula, n1 represents an integer from 1 to 10, which is the same as the above definition.)

[0336] CF2=CF-O-(CF2C(CF3)F) n2 -Y 3 (6b)

[0337] (In the formula, n2 represents an integer from 1 to 5, and Y 3 is the same as the above definition.)

[0338] CF2=CF-O-(CFX 1 ) n3 -Y 3 (6c)

[0339] (In the formula, X 1 represents F or CF3, n3 represents an integer from 1 to 10, and Y 3Same as the above definition.)

[0340] CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -Y 3 (6d)

[0341] (In the formula, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, Y 3 and X 1 are the same as the above definitions.)

[0342] CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-Y 3 (6e)

[0343] (In the formula, n5 represents an integer of 0 to 10, Y 3 and X 1 are the same as the above definitions.)

[0344] In the general formula (6a), the above-mentioned n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. From the viewpoints of obtaining appropriate water solubility and excellent sedimentation stability of the composition, the above-mentioned Y 3 is preferably -COOM. From the viewpoints of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M is preferably H or NH4.

[0345] Examples of the compound represented by the general formula (6a) include CF2=CF-O-CF2COOM, CF2=CF(OCF2CF2COOM), and CF2=CF(OCF2CF2CF2COOM) (wherein M is the same as the above definition).

[0346] In the general formula (6b), from the viewpoint of the sedimentation stability of the obtained composition, the above-mentioned n2 is preferably an integer of 3 or less. From the viewpoints of obtaining appropriate water solubility and excellent sedimentation stability of the composition, Y 3 is preferably -COOM. From the viewpoints of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M is preferably H or NH4.

[0347] In the general formula (6c), from the viewpoint of water solubility, the above-mentioned n3 is preferably an integer of 5 or less. From the viewpoints of obtaining appropriate water solubility and excellent sedimentation stability of the composition, the above-mentioned Y 3 is preferably -COOM. From the viewpoint of improving sedimentation stability, the above-mentioned M is preferably H or NH4.

[0348] In general formula (6d), from the viewpoint of the sedimentation stability of the composition, the above-mentioned X 1 is preferably -CF3. From the viewpoint of water solubility, the above-mentioned n4 is preferably an integer of 5 or less. From the viewpoint of obtaining moderate water solubility and excellent sedimentation stability of the composition, the above-mentioned Y 3 is preferably -COOM, and the above-mentioned M is preferably H or NH4.

[0349] Examples of the compound represented by general formula (6d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2COOM, and CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM (wherein M represents H, NH4, or an alkali metal).

[0350] In general formula (6e), from the viewpoint of water solubility, the above-mentioned n5 is preferably an integer of 5 or less. From the viewpoint of obtaining moderate water solubility and excellent sedimentation stability of the composition, the above-mentioned Y 3 is preferably -COOM, and the above-mentioned M is preferably H or NH4.

[0351] Examples of the compound represented by general formula (6e) include CF2=CFOCF2CF2CF2COOM (wherein M represents H, NH4, or an alkali metal).

[0352] In general formula (7A), Rf is preferably a fluoroalkylene group having 1 to 40 carbon atoms. In general formula (7A), at least one of X and Y preferably contains a fluorine atom.

[0353] The compound represented by general formula (7A) is preferably selected from the group consisting of general formula (7a):

[0354] CF2=CF-(CF2) n1 -Y 3 (7a)

[0355] (wherein n1 represents an integer of 1 to 10, and Y 3 is as defined above), and general formula (7b):

[0356] CF2=CF-(CF2C(CF3)F) n2 -Y 3 (7b)

[0357] (wherein n2 represents an integer of 1 to 5, and Y 3 is as defined above).

[0358] The above-mentioned Y 3Preferably -SO3M or -COOM, and M is preferably H, a metal atom, NR 7 4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. The above R 7 represents H or an organic group.

[0359] In the general formula (7a), the above n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. From the aspect of obtaining moderate water solubility and excellent sedimentation stability of the composition, the above Y 3 is preferably -COOM. From the aspect that it is difficult to remain as an impurity and the heat resistance of the obtained molded body is improved, M is preferably H or NH4. As the compound represented by the general formula (7a), for example, CF2=CFCF2COOM (wherein, M is the same as defined above) can be cited.

[0360] In the general formula (7b), from the aspect of the sedimentation stability of the obtained composition, the above n2 is preferably an integer of 3 or less. From the aspect of obtaining moderate water solubility and excellent sedimentation stability of the composition, Y 3 is preferably -COOM. From the aspect that it is difficult to remain as an impurity and the heat resistance of the obtained molded body is improved, M is preferably H or NH4.

[0361] The modified monomer preferably contains the modified monomer (A), preferably contains at least one selected from the group consisting of the compounds represented by the general formula (5a), the general formula (5b), the general formula (6a), the general formula (6b), the general formula (6c), and the general formula (6d), and more preferably contains the compound represented by the general formula (5a) or the general formula (5b).

[0362] When the modified monomer contains the above modified monomer (A), the content of the modified monomer (A) unit is preferably in the range of 0.00001% by mass to 1.0% by mass with respect to all the polymerization units of PTFE. As the lower limit, it is preferably 0.0001% by mass, more preferably 0.001% by mass, further preferably 0.005% by mass, and particularly preferably 0.009% by mass. As the upper limit, in the order of preference, they are 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, 0.08% by mass, 0.05% by mass, and 0.01% by mass.

[0363] In the present invention, the content of each compound unit constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of the compound. In addition, the content of each compound unit constituting PTFE can also be obtained by calculation from the addition amount of the modified monomer used in the polymerization.

[0364] PTFE can have a core-shell structure. As PTFE having a core-shell structure, for example, modified PTFE containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE in the particles can be cited. As such modified PTFE, for example, PTFE described in Japanese Patent Application Laid-Open No. 2005-527652 can be cited.

[0365] The average primary particle diameter of PTFE is preferably 150 nm or more, more preferably 180 nm or more. The larger the average primary particle diameter of PTFE, the more the increase in the paste extrusion pressure can be suppressed during paste extrusion molding using its powder, and the more excellent the film-forming property. The upper limit is not particularly limited and can be 500 nm. From the aspect of productivity in the polymerization process, the upper limit is preferably 400 nm, more preferably 350 nm. Regarding the above average primary particle diameter, the PTFE aqueous dispersion is diluted with water to a solid content concentration of 0.15% by mass, and the transmittance of the 550 nm transmitted light per unit length of the obtained diluted emulsion and the number-based length average primary particle diameter determined by measuring the orientation diameter from a transmission electron microscope photograph are measured to prepare a calibration curve, and the measured transmittance of the 550 nm transmitted light of each sample is used to determine using this calibration curve.

[0366] In addition, the above average primary particle diameter can be measured by dynamic light scattering method. Regarding the above average primary particle diameter, an aqueous dispersion having a solid content concentration adjusted to about 1.0% by mass can be prepared, and measurement is carried out under the conditions of 25 °C, a refractive index of the solvent (water) of 1.3328, a viscosity of the solvent (water) of 0.8878 mPa·s, and a cumulative 70 times using the dynamic light scattering method. As the dynamic light scattering method, for example, ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) can be used.

[0367] The aspect ratio of the primary particles of PTFE is preferably less than 2.00, more preferably 1.90 or less, further preferably 1.80 or less, still more preferably 1.70 or less, particularly preferably 1.60 or less, and most preferably 1.50 or less. The aspect ratio is more preferably 1.45 or less, further preferably 1.40 or less, still more preferably 1.35 or less, particularly preferably 1.30 or less, most preferably 1.20 or less, and extremely preferably 1.10 or less. When measured in an aqueous dispersion, the aspect ratio is determined as follows: The PTFE aqueous dispersion with a solid component concentration diluted to about 1% by mass is observed using a scanning electron microscope (SEM), image processing is performed on 400 or more randomly selected particles, and the average of the ratio of the major axis to the minor axis is obtained. When measured using powder, the aspect ratio is determined as follows: After irradiating the PTFE powder with electron rays, it is added to an aqueous solution of a fluorine-based surfactant and redispersed using ultrasonic waves to obtain a PTFE aqueous dispersion. The aspect ratio is obtained from this PTFE aqueous dispersion using the same method as the method for measuring through the aqueous dispersion.

[0368] The standard specific gravity (SSG) of PTFE is preferably 2.280 or less, more preferably 2.210 or less, further preferably 2.200 or less, still more preferably 2.190 or less, and particularly preferably 2.180 or less. Additionally, it is preferably 2.130 or more. The SSG is measured using a sample molded according to ASTM D 4895-89 by the water displacement method according to ASTM D 792.

[0369] The peak temperature of PTFE preferably exists in the range of 333 °C to 347 °C. More preferably, it is 335 °C or higher and 345 °C or lower. Regarding the above peak temperature, for PTFE that has not been heated to a temperature of 300 °C or higher, it is heated at a rate of 10 °C / minute using a differential scanning calorimeter [DSC], and it is the temperature corresponding to the maximum value in the heat of fusion curve at this time. Additionally, regarding the peak temperature, using a TG / DTA (simultaneous differential thermal and thermogravimetric analyzer) to heat PTFE that has not been heated to a temperature of 300 °C or higher at a rate of 10 °C / minute, it can be specified as the temperature corresponding to the maximum value that appears in the differential thermal (DTA) curve obtained therefrom.

[0370] As the content of PTFE in the composition of the present invention, relative to the composition, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more. The upper limit of the content of PTFE in the composition is not particularly limited and can be 80% by mass or less, can be 75% by mass or less, or can also be 70% by mass or less. Means such as concentration and dilution can be used to adjust the content of PTFE in the composition.

[0371] The content of PTFE in the composition of the present invention can be determined by measuring the solid component concentration of the composition, the content of polymer (I) in the composition, and the content of nonionic surfactant in the composition, and subtracting the content of polymer (I) and nonionic surfactant from the solid component concentration of the composition. Regarding the solid component concentration of the composition, 1 g of the composition is dried in a blast dryer at 150 °C for 30 minutes, the mass of the heating residue is measured, and the ratio of the mass of the heating residue to the mass of the composition (1 g) is calculated as a percentage, which is the value obtained thereby. The measurement methods for the content of polymer (I) and nonionic surfactant are as described in the examples.

[0372] In addition, the content of polymer (I) contained in the composition of the present invention is determined by solid-state NMR measurement.

[0373] In addition, the measurement methods of various polymers are described in International Publication No. WO2014 / 099453, International Publication No. WO2010 / 075497, International Publication No. WO2010 / 075496, International Publication No. WO2011 / 008381, International Publication No. WO2009 / 055521, International Publication No. WO1987 / 007619, Japanese Patent Application Laid-Open No. JP61-293476, International Publication No. WO2010 / 075494, International Publication No. WO2010 / 075359, International Publication No. WO2012 / 082454, International Publication No. WO2006 / 119224, International Publication No. WO2013 / 085864, International Publication No. WO2012 / 082707, International Publication No. WO2012 / 082703, International Publication No. WO2012 / 082454, International Publication No. WO2012 / 082451, International Publication No. WO2006 / 135825, International Publication No. WO2004 / 067588, International Publication No. WO2009 / 068528, Japanese Patent Application Laid-Open No. JP2004-075978, Japanese Patent Application Laid-Open No. JP2001-226436, International Publication No. WO1992 / 017635, International Publication No. WO2014 / 069165, Japanese Patent Application Laid-Open No. JP11-181009, etc. As the measurement method for the content of polymer (I), the measurement methods of various polymers described in these documents can be used.

[0374] <Polymer (I)>

[0375] The composition of the present invention contains polymer (I). Polymer (I) contains polymerization unit (I) based on the monomer represented by general formula (I). Polymer (I) preferably contains two or more polymerization units (I).

[0376] CX 1 X3 = CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0377] (wherein, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, an alkyl group or a fluoroalkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluoroalkyl group; m is an integer of 1 or more.)

[0378] As X 2 , preferably F, Cl, H or CF3. Further, as Z 1 and Z 2 , preferably F or CF3.

[0379] In the present invention, the anionic group includes not only anionic groups such as a sulfate group and a carboxylate group, but also functional groups that provide an anionic group such as an acid group like -COOH and a salt group like -COONH4. As the anionic group, preferably a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group or -C(CF3)2OM (wherein, M is -H, a metal atom, -NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents or a phosphonium with or without substituents, and R 7 is H or an organic group).

[0380] The polymer (I) may contain only the polymerization unit (I) based on one kind of monomer represented by the general formula (I), or may contain the polymerization unit (I) based on two or more kinds of monomers represented by the general formula (I).

[0381] R is a linking group. In the present invention, the "linking group" is a (m + 1)-valent linking group, and when m is 1, it refers to a divalent linking group. The linking group may be a single bond, preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, may be 4 or more, may be 8 or more, may be 10 or more, and may also be 20 or more. There is no upper limit, for example, it may be 100 or less, or may be 50 or less.

[0382] The linking group can be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and may contain, as desired, one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may contain, as desired, one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, carbamate, urea, and urethane. The above linking group does not contain carbon atoms and can be a linear heteroatom such as oxygen, sulfur, or nitrogen.

[0383] m is an integer of 1 or more, preferably 1 or 2, more preferably 1. When m is an integer of 2 or more, Z 1 、Z 2 and A 0 can be the same or different.

[0384] Next, the preferred constitution when m is 1 in the general formula (I) will be described.

[0385] R is preferably a linear heteroatom such as oxygen, sulfur, nitrogen, or a divalent organic group.

[0386] When R is a divalent organic group, the hydrogen atom bonded to the carbon atom can be replaced by a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. In addition, R can be either linear or branched, and can be either cyclic or acyclic. In addition, R can contain functional groups (such as ester, ether, ketone, amine, halide, etc.).

[0387] In addition, R can be a non-fluorinated divalent organic group, or a partially fluorinated or perfluorinated divalent organic group.

[0388] Examples of R include: a hydrocarbon group in which no fluorine atom is bonded to the carbon atom; a hydrocarbon group in which a part of the hydrogen atoms bonded to the carbon atom are replaced by fluorine atoms; or a hydrocarbon group in which all of the hydrogen atoms bonded to the carbon atom are replaced by fluorine atoms, and they can contain oxygen atoms, can contain double bonds, and can also contain functional groups.

[0389] R is preferably a hydrocarbon group having 1 to 100 carbon atoms with or without an ether bond, and in this hydrocarbon group, a part or all of the hydrogen atoms bonded to the carbon atoms can be replaced by fluorine.

[0390] Examples of R preferably include those selected from -(CH2) a -、-(CF2) a -、-O-(CF2) a -、-(CF2) a -O-(CF2) b -、-O(CF2) a -O-(CF2) b -、-(CF2) a -[O-(CF2) b ​c -,-O(CF2) a -[O-(CF2) b c -,-[(CF2) a -O] b -[(CF2) c -O] d -,-O[(CF2) a -O] b -[(CF2) c -O] d -,-O-[CF2CF(CF3)O] a -(CF2) b -,-[CF2CF(CF3)O] a -,-[CF(CF3)CF2O] a -,-(CF2) a -O-[CF(CF3)CF2O] a -,-(CF2) a -O-[CF(CF3)CF2O] a -(CF2) b - and at least one of their combinations.

[0391] In the formula, a, b, c and d are independently at least 1 or more. a, b, c and d can independently be 2 or more, can be 3 or more, can be 4 or more, can be 10 or more, or can be 20 or more. The upper limit of a, b, c and d is, for example, 100.

[0392] As R, the general formula (r1) is preferred:

[0393] -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g - (r1)

[0394] (In the formula, X 6 are each independently H, F or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, and g is 0 or 1), the divalent group shown, and the general formula (r2) is preferred:

[0395] -CF2-O-(CX 7 2) e -(O) g - (r2)

[0396] (In the formula, X 7 are each independently H, F or CF3, e is an integer from 0 to 3, and g is 0 or 1), the divalent group shown. ​

[0397] Specific examples preferably used as R include -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CH2-, etc. Among them, R preferably represents a perfluoroalkylene group which may or may not contain an oxygen atom. Specifically, -CF2-O-, -CF2-O-CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, or -CF2-O-CF(CF3)CF2-O- is preferred.

[0398] As -R-CZ in the general formula (I) 1 Z 2 -, preferably the general formula (s1):

[0399] -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 - (s1)

[0400] (In the formula, X 6 are each independently H, F or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, Z 1 and Z 2 are each independently H, F, an alkyl group or a fluoroalkyl group), in the formula (s1), Z 1 and Z 2 are more preferably F or CF3, and still more preferably one is F and the other is CF3.

[0401] In addition, in the general formula (I), as -R-CZ 1 Z 2 -, preferably the general formula (s2):

[0402] -CF2-O-(CX 7 2) e -(O) g -CZ 1 Z 2 - (s2)

[0403] (In the formula, X7 Each independently is H, F or CF3, e is an integer from 0 to 3, g is 0 or 1, Z 1 and Z 2 Each independently is a divalent group represented by H, F, alkyl or fluoroalkyl), in formula (s2), Z 1 and Z 2 Is more preferably F or CF3, and still more preferably one is F and the other is CF3.

[0404] As -R-CZ of general formula (I) 1 Z 2 -, preferably -CF2-O-CF2-, -CF2-O-CF(CF3)-, -CF2-O-C(CF3)2-, -CF2-O-CF2-CF2-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2-C(CF3)2-, -CF2-O-CF2CF2-CF2-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF2CF2-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)CF2-CF2-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-C(CF3)2-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, or -CF2-O-CF(CF3)CF2-O-C(CF3)2-, more preferably -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)CF2-CF(CF3)-, or -CF2-O-CF(CF3)CF2-O-CF(CF3)-.

[0405] Polymer (I) is also preferably highly fluorinated. For example, it is preferably free of anionic groups (A such as phosphate ester groups (e.g., CH2OP(O)(OM)2) and sulfate ester groups (e.g., CH2OS(O)2OM) 0)In addition, more than 80%, more than 90%, more than 95%, or 100% of the C-H bonds in the polymer (I) are replaced by C-F bonds.

[0406] The polymer (I) also preferably has C-F bonds and no C-H bonds except for the anionic group (A 0 ). That is, in the general formula (I), it is preferred that X 1 , X 2 , and X 3 are all F, R is a perfluoroalkylene group having 1 or more carbon atoms, the above perfluoroalkylene group can be either linear or branched, can be either cyclic or acyclic, and can contain at least 1 chain-like heteroatom. The number of carbon atoms of the above perfluoroalkylene group can be 2-20, or can be 4-18.

[0407] The polymer (I) can also be partially fluorinated. That is, the polymer (I) also preferably has at least 1 hydrogen atom bonded to a carbon atom and at least 1 fluorine atom bonded to a carbon atom except for the anionic group (A 0 ).

[0408] The anionic group (A 0 ) can be -SO3M, -OSO3M, -COOM, -SO2NR’CH2COOM, -CH2OP(O)(OM)2, [-CH2O]2P(O)(OM), -CH2CH2OP(O)(OM)2, [-CH2CH2O]2P(O)(OM), -CH2CH2OSO3M, -P(O)(OM)2, -SO2NR’CH2CH2OP(O)(OM)2, [-SO2NR’CH2CH2O]2P(O)(OM), -CH2OSO3M, -SO2NR’CH2CH2OSO3M, or -C(CF3)2OM. Among them, -SO3M, -COOM or -P(O)(OM)2 is preferred, -SO3M or -COOM is more preferred, and -COOM is further preferred.

[0409] M is H, a metal atom, NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 7 is H or an organic group.

[0410] Examples of the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.

[0411] As M, -H, a metal atom or -NR 7 4 is preferred, and -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 74. Further preferably, it is -H, -Na, -K, -Li or -NH4, still more preferably -Na, -K or -NH4, particularly preferably -Na or -NH4, and most preferably -NH4.

[0412] In the polymer (I), each polymerization unit (I) may have different anionic groups or may have the same anionic group.

[0413] The polymer (I) is also preferably a polymer containing a polymerization unit (Ia) based on the monomer represented by the general formula (Ia).

[0414] CF2=CF-O-Rf 0 -A 0 (Ia)

[0415] (In the formula, A 0 is an anionic group, and Rf 0 is perfluorinated, and can be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and is an optionally additionally containing one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen perfluorinated divalent linking group.)

[0416] The above polymer (I) is also preferably a polymer containing a polymerization unit (Ib) based on the monomer represented by the general formula (Ib).

[0417] CH2=CH-O-Rf 0 -A 0 (Ib)

[0418] (In the formula, A 0 is an anionic group, and Rf 0 is the perfluorinated divalent linking group defined in formula Ia.)

[0419] In the general formula (I), A 0 being a sulfate group is one of the preferred embodiments. A 0 For example, it is -CH2OSO3M, -CH2CH2OSO3M or -SO2NR’CH2CH2OSO3M, in the formula, R’ is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0420] A 0When it is a sulfate group, as the monomer represented by the general formula (I), for example, CF2=CF(OCF2CF2CH2OSO3M), CH2=CH((CF2)4CH2OSO3M), CF2=CF(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF(CF3)CH2OSO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M), CH2=CH((CF2)4CH2OSO3M), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CF2CH2OSO3M) etc. can be cited. In the above formula, M is the same as described above.

[0421] In the general formula (I), A 0 being a sulfonate group is also one of the preferred modes. As A 0 , for example, it is -SO3M, and in the formula, M is the same as described above.

[0422] When A 0 is a sulfonate group, as the monomer represented by the general formula (I), CF2=CF(OCF2CF2SO3M), CF2=CF(O(CF2)3SO3M), CF2=CF(O(CF2)4SO3M), CF2=CF(OCF2CF(CF3)SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M), CH2=CH(CF2CF2SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M), CH2=CH((CF2)4SO3M), CH2=CH(CF2CF2SO3M), CH2=CH((CF2)3SO3M) etc. can be cited. In the above formula, M is the same as described above.

[0423] In the general formula (I), A 0 being a carboxylate group is also one of the preferred modes. As A 0 , for example, it is -COOM or -SO2NR’CH2COOM, where R’ is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as described above. When A 0When it is a carboxylic acid ester group, as the monomer represented by the general formula (I), CF2=CF(OCF2CF2COOM), CF2=CF(O(CF2)3COOM), CF2=CF(O(CF2)4COOM), CF2=CF(O(CF2)5COOM), CF2=CF(OCF2CF(CF3)COOM), CF2=CF(OCF2CF(CF3)O(CF2) n COOM) (n is greater than 1), CH2=CH(CF2CF2COOM), CH2=CH((CF2)4COOM), CH2=CH(CF2CF2COOM), CH2=CH((CF2)3COOM), CF2=CF(OCF2CF2SO2NR’CH2COOM), CF2=CF(O(CF2)4SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM), CH2=CH(CF2CF2SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM), CH2=CH((CF2)4SO2NR’CH2COOM), CH2=CH(CF2CF2SO2NR’CH2COOM), CH2=CH((CF2)3SO2NR’CH2COOM), etc. In the above formula, R’ is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0424] In the general formula (I), A 0 being a phosphate group is also one of the preferred modes. As A 0 , for example, it is -CH2OP(O)(OM)2, [-CH2O]2P(O)(OM), -CH2CH2OP(O)(OM)2, [-CH2CH2O]2P(O)(OM), [-SO2NR’CH2CH2O]2P(O)(OM) or -SO2NR’CH2CH2OP(O)(OM)2. In the formula, R’ is an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0425] In A 0When it is a phosphate ester, as the monomer represented by the general formula (I), examples include CF2=CF(OCF2CF2CH2OP(O)(OM)2), CF2=CF(O(CF2)4CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CH2=CH(CF2CF2CH2OP(O)(OM)2), CH2=CH((CF2)4CH2OP(O)(OM)2), CH2=CH(CF2CF2CH2OP(O)(OM)2), CH2=CH((CF2)3CH2OP(O)(OM)2), etc. In the above formula, M is the same as described above.

[0426] In the general formula (I), A 0 being a phosphonate group is also one of the preferred embodiments. When A 0 is a phosphonate group, as the monomer represented by the general formula (I), examples include CF2=CF(OCF2CF2P(O)(OM)2), CF2=CF(O(CF2)4P(O)(OM)2), CF2=CF(OCF2CF(CF3)P(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2), CH2=CH(CF2CF2P(O)(OM)2), CH2=CH((CF2)4P(O)(OM)2), CH2=CH(CF2CF2P(O)(OM)2), CH2=CH((CF2)3P(O)(OM)2), where M is the same as described above.

[0427] The polymer (I) is preferably a polymer (1) containing a polymerization unit (1) based on the monomer represented by the general formula (1).

[0428] CX2=CY(-CZ2-O-Rf-A)(1)

[0429] (In the formula, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluoroalkyl group, Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group. Rf is a fluoroalkylene group having 1 to 40 carbon atoms, or a fluoroalkylene group having an ether bond and 2 to 100 carbon atoms. A is -COOM, -SO3M, -OSO3M or C(CF3)2OM (M is -H, a metal atom, -NR 74. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7 is H or an organic group. At least one of X, Y, and Z contains a fluorine atom.)

[0430] By including the polymer (1) in the composition of the present invention, the sedimentation stability of the composition is further improved. In addition, when manufacturing a composition containing PTFE using the polymer (I), by using the polymer (1) as the polymer (I), the composition can be manufactured more stably and efficiently. In addition, high-molecular-weight PTFE can be obtained in a high yield. It should be noted that the fluoroalkylene group having an ether bond with 2 to 100 carbon atoms is an alkylene group that does not have an oxygen atom at the end and contains an ether bond between carbon-carbon atoms.

[0431] In the general formula (1), X is -H or -F. Both X can be -F, or at least one of them can be -H. For example, one can be -F and the other can be -H, or both can be -H.

[0432] In the general formula (1), Y is -H, -F, an alkyl group, or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above fluoroalkyl group is an alkyl group that contains at least one fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. As the above Y, -H, -F, or -CF3 is preferred, and -F is more preferred.

[0433] In the general formula (1), Z is the same or different and is -H, -F, an alkyl group, or a fluoroalkyl group. The above alkyl group is an alkyl group that does not contain a fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. The above fluoroalkyl group is an alkyl group that contains at least one fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. As the above Z, -H, -F, or -CF3 is preferred, and -F is more preferred.

[0434] In the general formula (1), at least one of the above X, Y, and Z contains a fluorine atom. For example, X can be -H, and Y and Z can be -F.

[0435] In the general formula (1), the above Rf is a fluoroalkylene group having 1 to 40 carbon atoms, or a fluoroalkylene group having 2 to 100 carbon atoms and having an ether bond.

[0436] The number of carbon atoms of the above-mentioned fluoroalkylene group is preferably 2 or more. Additionally, the number of carbon atoms of the above-mentioned fluoroalkylene group is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less. Examples of the above-mentioned fluoroalkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The above-mentioned fluoroalkylene group is preferably a perfluoroalkylene group.

[0437] The number of carbon atoms of the above-mentioned fluoroalkylene group having an ether bond is preferably 3 or more. Additionally, the number of carbon atoms of the above-mentioned fluoroalkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and further preferably 12 or less. The above-mentioned fluoroalkylene group having an ether bond is also preferably, for example, of the general formula:

[0438]

Chemical Formula 12

[0439]

[0440] (In the formula, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; p1 + q1 + r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5) represents a divalent group.

[0441] Examples of the above-mentioned fluoroalkylene group having an ether bond specifically include -CF(CF3)CF2 - O - CF(CF3)-, -(CF(CF3)CF2 - O) n -CF(CF3)-(where n is an integer from 1 to 10), -CF(CF3)CF2 - O - CF(CF3)CH2-, -(CF(CF3)CF2 - O) n -CF(CF3)CH2-(where n is an integer from 1 to 10), -CH2CF2CF2O - CH2CF2CH2-, -CF2CF2CF2O - CF2CF2-, -CF2CF2CF2O - CF2CF2CH2-, -CF2CF2O - CF2-, -CF2CF2O - CF2CH2-, etc. The above-mentioned fluoroalkylene group having an ether bond is preferably a perfluoroalkylene group.

[0442] In the general formula (1), A is -COOM, -SO3M, -OSO3M or -C(CF3)2OM (M is -H, a metal atom, -NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 7 is H or an organic group).

[0443] As R 7 , preferably H or C 1-10 organic group, more preferably H or C 1-4 organic group, still more preferably H or C 1-4 alkyl group.

[0444] As the metal atom, alkali metals (Group 1), alkaline earth metals (Group 2), etc. can be mentioned, and Na, K or Li is preferred.

[0445] 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, still more preferably -H, -Na, -K, -Li or -NH4, still further preferably -Na, -K or -NH4, particularly preferably -Na or -NH4, and most preferably -NH4.

[0446] As A, -COOM or -SO3M is preferred, and -COOM is more preferred.

[0447] As the monomer represented by the general formula (1), for example, the general formula (1a) can be exemplified:

[0448] CX2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-A (1a)

[0449] (In the formula, each X is the same and represents F or H. n5 represents an integer of 0 or 1 to 10, and A has the same definition as above) fluorinated allyl ether compound.

[0450] In the general formula (1a), from the aspect of being able to obtain PTFE particles with a small primary particle size, n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1 or 2, and still more preferably 0 or 1.

[0451] The polymer (1) can be a homopolymer of the fluorinated allyl ether compound represented by the general formula (1a), or a copolymer with other monomers.

[0452] The polymerization unit (1) is preferably the polymerization unit (1A) based on the monomer represented by the general formula (1A).

[0453] CH2=CF(-CF2-O-Rf-A) (1A)

[0454] (In the formula, Rf and A are the same as above.)

[0455] The polymer (1) can be a homopolymer of the monomer represented by the general formula (1A), or a copolymer with other monomers.

[0456] As the monomer represented by the formula (1A), specifically, the general formula can be cited as

[0457]

Chemical Formula 13

[0458]

[0459] (In the formula, Z 1 is F or CF3; Z 2 and Z 3 are each H or F; Z 4 is H, F or CF3; pl + ql + rl is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, where, when both Z 3 and Z 4 are H, pl + ql + rl + s1 is not 0; A is as defined above) the monomer shown. More specifically, preferably, the following can be cited

[0460]

Chemical Formula 14

[0461]

[0462] CH2 = CFCF2OCH2CF2 - A, CH2 = CFCF2O(CH2CF2CF2O)CH2CF2 - A,

[0463] CH2 = CFCF2OCH2CF2CH2 - A,

[0464] CH2 = CFCF2O(CH2CF2CF2O)CH2CF2CH2 - A,

[0465] CH2 = CFCF2OCF2CF2 - A, CH2 = CFCF2O(CF2CF2CF2O)CF2CF2 - A,

[0466] CH2 = CFCF2OCF2CF2CH2 - A,

[0467] CH2 = CFCF2O(CF2CF2CF2O)CF2CF2CH2 - A,

[0468] CH2 = CFCF2OCF2 - A, OH2 = CFCF2O(CF2CF2O)CF2 - A,

[0469] CH2 = CFCF2OCF2CH2 - A,

[0470] CH2 = CFCF2O(CF2CF2O)CF2CH2 - A, etc., among which the preferred ones are

[0471]

Chemical Formula 15

[0472]

[0473] As the monomer represented by the general formula (1A), it is preferred that A in the formula (1A) is -COOM, and it is particularly preferred that at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is as defined above), and it is more preferred that CH2=CFCF2OCF(CF3)COOM.

[0474] In addition, as the monomer represented by the general formula (1), monomers represented by the following formula can also be cited.

[0475] CF2=CFCF2-O-Rf-A

[0476] (wherein, Rf and A are the same as above.)

[0477] More specifically, the following can be cited

[0478]

Chemical Formula 16

[0479] CF2=CFCF2OCF2CF2CF2-A,

[0480]

[0481] CF2=CFCF2OCF2CF2CF2CH2-A,

[0482] etc.

[0483] The polymer (I) is also preferably a polymer (2) containing a polymerization unit (2) based on the monomer represented by the general formula (2).

[0484] CX2=CY(-O-Rf-A) (2)

[0485] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluoroalkyl group, Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having an ether bond and having 2 to 100 carbon atoms. A is the same as above.)

[0486] In the general formula (2), X is -H or -F. Both X can be -F, or at least one of them can be -H. For example, one can be -F and the other can be -H, or both can be -H.

[0487] In general formula (2), Y is -H, -F, an alkyl group, or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain fluorine atoms, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The fluoroalkyl group is an alkyl group that contains at least 1 fluorine atom, and it is sufficient that the number of carbon atoms is 1 or more. The number of carbon atoms of the above fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. As Y, -H, -F, or -CF3 is preferred, and -F is more preferred.

[0488] In general formula (2), at least one of the above X and Y preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0489] In general formula (2), the above Rf is a fluoroalkylene group having 1 to 40 carbon atoms, or a fluoroalkylene group having an ether bond and 2 to 100 carbon atoms. It should be noted that the fluoroalkylene group having an ether bond and 2 to 100 carbon atoms is an alkylene group that does not contain a structure with an oxygen atom at the end and contains an ether bond between carbon atoms.

[0490] The number of carbon atoms of the fluoroalkylene group of Rf is preferably 2 or more. In addition, it is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less. Examples of the fluoroalkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The fluoroalkylene group is preferably a perfluoroalkylene group.

[0491] The monomer represented by general formula (2) is preferably at least one selected from the group consisting of the monomers represented by general formulas (2a), (2b), (2c), (2d), and (2e).

[0492] CF2=CF-O-(CF2) n1 -A (2a)

[0493] (In the formula, n1 represents an integer from 1 to 10, and A is the same as above.)

[0494] CF2=CF-O-(CF2C(CF3)F) n2 -A (2b)

[0495] (In the formula, n2 represents an integer from 1 to 5, and A has the same definition as above.)

[0496] CF2=CF-O-(CFX 1 ) n3 -A (2c)

[0497] (In the formula, X 1represents F or CF3, n3 represents an integer from 1 to 10, Y 3 is the same as the above definition.)

[0498] CF2=CF-O-(CF2CFX 1 O) n4 -(CF2) n6 -A (2d)

[0499] (wherein, n4 represents an integer from 1 to 10, n6 represents an integer from 1 to 3, A and X 1 are the same as the above definition.)

[0500] CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-A (2e)

[0501] (wherein, n5 represents an integer from 0 to 10, A and X 1 are the same as the above definition.)

[0502] In the general formula (2a), the above-mentioned n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less.

[0503] As the monomer represented by the general formula (2a), for example, CF2=CF-O-CF2COOM, CF2=CF(OCF2CF2COOM), CF2=CF(O(CF2)3COOM), CF2=CF(OCF2CF2SO3M) (wherein, M is the same as the above definition) can be cited.

[0504] In the general formula (2b), from the viewpoint of the sedimentation stability of the obtained composition, n2 is preferably an integer of 3 or less.

[0505] In the general formula (2c), from the viewpoint of water solubility, n3 is preferably an integer of 5 or less, the above-mentioned A is preferably -COOM, and the above-mentioned M is preferably H or NH4.

[0506] In the general formula (2d), from the viewpoint of the sedimentation stability of the composition, X 1 is preferably -CF3, from the viewpoint of water solubility, n4 is preferably an integer of 5 or less, A is preferably -COOM, and M is preferably H or NH4.

[0507] As the monomer represented by the general formula (2d), for example, CF2=CFOCF2CF(CF3)OCF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2COOM, CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM (wherein, M represents H, NH4 or an alkali metal) can be cited.

[0508] In general formula (2e), from the aspect of water solubility, n5 is preferably an integer of 5 or less, A is preferably -COOM, and M is preferably H or NH4.

[0509] Examples of the monomer represented by general formula (2e) include CF2=CFOCF2CF2CF2COOM (wherein M represents H, NH4 or an alkali metal).

[0510] Polymer (I) is also preferably a polymer (3) containing a polymerization unit (3) based on the monomer represented by general formula (3).

[0511] CX2=CY(-Rf-A) (3)

[0512] (wherein X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluoroalkyl group, and Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having an ether bond and 2 to 100 carbon atoms. A is the same as above.)

[0513] It should be noted that the fluoroalkylene group having an ether bond and 2 to 100 carbon atoms does not include a structure with an oxygen atom at the end but includes an ether bond between carbon-carbon atoms.

[0514] In general formula (3), Rf is preferably a fluoroalkylene group having 1 to 40 carbon atoms. In general formula (3), at least one of X and Y preferably contains a fluorine atom.

[0515] The monomer represented by general formula (3) is preferably selected from the group consisting of general formula (3a):

[0516] CF2=CF-(CF2) n1 -A (3a)

[0517] (wherein n1 represents an integer of 1 to 10, and A has the same definition as above) and general formula (3b):

[0518] CF2=CF-(CF2C(CF3)F) n2 -A (3b)

[0519] (wherein n2 represents an integer of 1 to 5, and A has the same definition as above) and at least one monomer selected from the group consisting of the monomers.

[0520] In general formulas (3a) and (3b), A is preferably -SO3M or -COOM, and M is preferably H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. R 7 represents H or an organic group.

[0521] In general formula (3a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. A is preferably -COOM, and M is preferably H or NH4.

[0522] Examples of the monomer represented by general formula (3a) include CF2=CFCF2COOM (wherein M has the same definition as above).

[0523] In general formula (3b), from the viewpoint of the sedimentation stability of the resulting composition, n2 is preferably an integer of 3 or less, A is preferably -COOM, and M is preferably H or NH4.

[0524] Next, the preferred configuration when m is an integer of 2 or more in general formula (I) will be described.

[0525] Polymer (I) is also preferably polymer (4), and the polymer (4) contains a polymerization unit (4) based on at least one monomer selected from the group consisting of monomers represented by general formula (4a) and general formula (4b).

[0526] CF2=CF-CF2-O-Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2 (4a)

[0527] (wherein Z 1 、Z 2 and A have the same definitions as above, and Q F1 and Q F2 are the same or different and are a single bond, a fluorinated alkylene group containing or not containing an ether bond between carbon atoms, or a fluorinated oxyalkylene group containing or not containing an ether bond between carbon atoms.)

[0528] CF2=CF-O-Q F1 -CF(-Q F2 -CZ 1 Z 2 -A)2 (4b)

[0529] (wherein Z 1 、Z 2 、A, Q F1 and Q F2 have the same definitions as above)

[0530] Examples of the monomers represented by general formula (4a) and general formula (4b) include

[0531]

Chemical Formula 17

[0532] etc.

[0533] Polymer (I) is preferably at least one selected from the group consisting of the above-mentioned polymers (1), (2), and (3), more preferably polymer (1).

[0534] Polymer (I) can be a homopolymer composed only of polymerization unit (I), or a copolymer containing polymerization unit (I) and polymerization units based on other monomers capable of copolymerizing with the monomer represented by the general formula (I). From the perspective of solubility in an aqueous medium, a homopolymer composed only of polymerization unit (I) is preferred. The polymerization unit (I) can be the same or different each time it appears, and polymer (I) can contain polymerization units (I) based on two or more different monomers represented by the general formula (I).

[0535] As the above-mentioned other monomers, fluorinated ethylenically unsaturated monomers having 2 or 3 carbon atoms are preferred, and examples thereof include CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E isomer), CHF=CHCF3 (Z isomer), etc.

[0536] Among them, from the aspect of good copolymerizability, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2) is preferred, and tetrafluoroethylene is more preferred. Therefore, the polymerization unit based on the above-mentioned other monomers is preferably a polymerization unit based on tetrafluoroethylene. The polymerization unit based on the above-mentioned other monomers can be the same or different each time it appears, and polymer (I) can contain polymerization units based on two or more different other monomers.

[0537] In addition, as the above-mentioned other monomers, the general formula (n1-2) can be cited:

[0538]

Chemical Formula 18

[0539]

[0540] (In the formula, X 1 , X 2 are the same or different and are H or F; X 3 is H, F, Cl, CH3, or CF3; X 4 , X 5 are the same or different and are H or F; a and c are the same or different and are 0 or 1. Rf 3 is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond and 2 to 100 carbon atoms) monomers.

[0541] Specifically, preferably, CH2=CFCF2-O-Rf 3, CF2=CF-O-Rf 3 , CF2=CFCF2-O-Rf 3 , CF2=CF-Rf 3 , CH2=CH-Rf 3 , CH2=CH-O-Rf 3 (In the formula, Rf 3 is the same as the above formula (n1-2), etc.)

[0542] As the above other monomers, the formula (n2-1) can also be cited:

[0543] [Chemical formula 19]

[0544]

[0545] (In the formula, X 9 is H, F or CH3; Rf 4 is a fluoroalkyl group having 1 to 40 carbon atoms or a fluoroalkyl group having an ether bond and 2 to 100 carbon atoms) the fluoroacrylate monomer shown. The above Rf 4 group can be cited as

[0546] [Chemical formula 20]

[0547]

[0548] (In the formula, Z 8 is H, F or Cl; d1 is an integer from 1 to 4; e1 is an integer from 1 to 10),

[0549] -CH(CF3)2,

[0550]

[0551] (In the formula, e2 is an integer from 1 to 5),

[0552]

[0553] (In the formula, d3 is an integer from 1 to 4; e3 is an integer from 1 to 10), etc.)

[0554] As the above other monomers, the formula (n2-2) can also be cited:

[0555] CH2=CHO-Rf 5 (n2-2)

[0556] (In the formula, Rf 5 is a fluoroalkyl group having 1 to 40 carbon atoms or a fluoroalkyl group having an ether bond and 2 to 100 carbon atoms) the fluorovinyl ether shown.

[0557] As the monomer of the general formula (n2-2), specifically, preferably, examples thereof include

[0558] [Chemical formula 21]

[0559]

[0560] (wherein, Z 9 is H or F; e4 is an integer of 1 to 10),

[0561]

[0562] (wherein, e5 is an integer of 1 to 10),

[0563]

[0564] (wherein, e6 is an integer of 1 to 10), etc.

[0565] More specifically, examples thereof include

[0566] [Chemical formula 22]

[0567] CH2=CHOCH2CF2CF2H,

[0568]

[0569]

[0570] CH2=CHOCH2CF2CF3,

[0571] CH2=CHOCH2CF3,

[0572]

[0573]

[0574] , etc.

[0575] In addition, the fluorinated allyl ether represented by the general formula (n2-3):

[0576] CH2=CHCH2O-Rf 6 (n2-3)

[0577] (wherein, Rf 6 is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond and 2 to 100 carbon atoms), the fluorinated allyl ether represented by the general formula (n2-4):

[0578] CH2=CH-Rf 7 (n2-4)

[0579] (wherein, Rf 7 is a fluoroalkyl group having 1 to 40 carbon atoms or a fluoroalkyl group having an ether bond and 2 to 100 carbon atoms), and fluoro vinyl monomers represented thereby, etc.

[0580] As the monomers represented by the general formulas (n2-3) and (n2-4), specifically, there may be mentioned

[0581]

Chemical Formula 23

[0582] CH2=CHCH2OCH2CF2CF2H,

[0583]

[0584] CH2=CHCH2OCH2CF2CF3,

[0585] CH2=CHCH2OCH2CF3,

[0586] and other monomers.

[0587] The polymer (I) usually has end groups. The end groups are the end groups generated during polymerization. The representative end groups are independently selected from hydrogen, iodine, bromine, linear or branched alkyl groups, and linear or branched fluoroalkyl groups, and may optionally contain at least 1 linear heteroatom. The number of carbon atoms of the alkyl group or fluoroalkyl group is preferably 1 to 20. These end groups are usually generated by an initiator or a chain transfer agent used in the formation of the polymer (I), or are generated in a chain transfer reaction.

[0588] In the polymer (I), the content of the polymerization unit (I) is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, further preferably 5.0 mol% or more, still more preferably 10 mol% or more, particularly preferably 20 mol% or more, and especially preferably 30 mol% or more with respect to all the polymerization units. More preferably 40 mol% or more, further preferably 60 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and especially preferably substantially 100 mol%, and most preferably composed only of the polymerization unit (I).

[0589] In the polymer (I), the content of the polymerization units based on other monomers copolymerizable with the monomers represented by the general formula (I) is preferably 99.0 mol% or less, more preferably 97.0 mol% or less, still more preferably 95.0 mol% or less, still further preferably 90 mol% or less, particularly preferably 80 mol% or less, and especially preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 40 mol% or less, still further preferably 20 mol% or less, particularly preferably 10 mol% or less, and especially preferably substantially 0 mol%, and particularly especially preferably does not contain polymerization units based on other monomers.

[0590] The number-average molecular weight of the polymer (I) is preferably 0.1×10 4 or more, more preferably 0.2×10 4 or more, still more preferably 0.3×10 4 or more, still further preferably 0.4×10 4 or more, particularly preferably 0.5×10 4 or more, especially preferably 1.0×10 4 or more, particularly especially preferably 3.0×10 4 or more, and most preferably 3.1×10 4 or more. In addition, it is preferably 75.0×10 4 or less, more preferably 50.0×10 4 or less, still more preferably 40.0×10 4 or less, particularly preferably 30.0×10 4 or less, especially preferably 20.0×10 4 or less. The number-average molecular weight and the weight-average molecular weight are values obtained by calculating the molecular weight using monodisperse polystyrene as a standard by gel permeation chromatography (GPC). In addition, in the case where it cannot be measured by GPC, the number-average molecular weight of the polymer (I) can be determined from the correlation between the number-average molecular weight calculated from the number of end groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured according to JIS K 7210.

[0591] As the lower limit of the weight-average molecular weight of the polymer (I), in order of preference, it is 0.2×10 4 or more, 0.4×10 4 or more, 0.6×10 4 or more, 0.8×10 4 or more, 1.0×10 4 or more, 2.0×10 4 or more, 5.0×10 4 or more, 10.0×10 4 or more, 15.0×104 Above, 20.0×10 4 Above, 25.0×10 4 Above. In addition, as the upper limit of the weight-average molecular weight of polymer (I), in order of preference, it is 150.0×10 4 Below, 100.0×10 4 Below, 60.0×10 4 Below, 50.0×10 4 Below, 40.0×10 4 Below.

[0592] Polymer (I) preferably has an ion exchange ratio (IXR) of 53 or less. The above IXR is defined as the number of carbon atoms in the polymer main chain relative to the ionic groups. A precursor group that becomes ionic by hydrolysis (e.g., -SO2F) is not regarded as an ionic group for determining IXR.

[0593] The IXR is preferably 0.5 or more, more preferably 1 or more, further preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and especially preferably 8 or more. In addition, the IXR is more preferably 43 or less, further preferably 33 or less, and especially preferably 23 or less.

[0594] As the ion exchange capacity of polymer (I), in order of preference, it is 0.80 meg / g or more, 1.50 meg / g or more, 1.75 meg / g or more, 2.00 meg / g or more, 2.50 meg / g or more, 2.60 meg / g or more, 3.00 meg / g or more, 3.50 meg / g or more. The ion exchange capacity is the content of the ionic groups (anionic groups) of polymer (I), and is obtained by calculation from the composition of polymer (I).

[0595] In polymer (I), the ionic groups (anionic groups) are typically distributed along the polymer main chain. The above polymer (I) preferably contains a polymer main chain and repeating side chains bonded to the main chain, and the side chains preferably have ionic groups.

[0596] Polymer (I) preferably contains ionic groups having a pKa of less than 10, more preferably less than 7. The ionic groups of polymer (I) are preferably selected from the group consisting of sulfonates, carboxylates, phosphonates, and phosphates.

[0597] The terms "sulfonates, carboxylates, phosphonates, and phosphates" refer to their respective salts or the respective acids capable of forming salts. In the case of using salts, it is preferred that the salts are alkali metal salts or ammonium salts. The preferred ionic group is a sulfonate group.

[0598] The polymer (I) preferably has water solubility. Water solubility refers to the property of being easily dissolved or dispersed in an aqueous medium. A polymer (I) with water solubility, for example, cannot have its particle size measured by dynamic light scattering (DLS). On the other hand, a polymer (I) with non-water solubility, for example, can have its particle size measured by dynamic light scattering (DLS).

[0599] In addition to using the above monomers, the polymer (I) can be manufactured by methods known in the art.

[0600] As the content of the polymer (I) in the composition, relative to the composition, it is preferably 2000 mass ppm or less, more preferably 1500 mass ppm or less, further preferably 1000 mass ppm or less, particularly preferably 500 mass ppm or less, and most preferably 250 mass ppm or less. Additionally, as the content of the polymer (I) in the composition, relative to the composition, it is preferably 0.1 mass ppm or more, more preferably 0.5 mass ppm or more.

[0601] As the content of the polymer (I) in the composition, relative to PTFE, it is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, particularly preferably 0.05 mass% or more, and most preferably 0.10 mass% or more. Additionally, as the content of the polymer (I) in the composition, relative to PTFE, it is preferably 10 mass% or less, more preferably 5.0 mass% or less, further preferably 2.0 mass% or less, particularly preferably 1.0 mass% or less, and most preferably 0.50 mass% or less.

[0602] Additionally, as the content of the polymer (I) in the composition, relative to PTFE, it is preferably 0.30 mass% or less, more preferably 0.20 mass% or less, further preferably 0.15 mass% or less, particularly preferably 0.10 mass% or less, and most preferably 0.05 mass% or less.

[0603] As the content of the dimers and trimers of the monomer represented by the general formula (I) in the composition, relative to the polymer (I), it is preferably 1.0 mass% or less, more preferably 0.1 mass% or less, further preferably 0.01 mass% or less, particularly preferably 0.001 mass% or less, and most preferably 0.0001 mass% or less.

[0604] The content of the dimers and trimers of the monomer represented by the general formula (I) in the composition can be measured by the same method as the content of the dimers and trimers in the polymer (I) described below.

[0605] <Non-ionic surfactant>

[0606] The first composition and the third composition of the present invention contain nonionic surfactants. The second composition of the present invention preferably contains nonionic surfactants.

[0607] The above nonionic surfactants generally do not contain charged groups and have a hydrophobic part as a long-chain hydrocarbon. The hydrophilic part of the nonionic surfactant contains water-soluble functional groups such as a chain of ethylene ethers derived from the polymerization of ethylene oxide.

[0608] Examples of the nonionic surfactant include the following substances.

[0609] Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and their derivatives.

[0610] Specific examples of polyoxyethylene alkyl ethers: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, etc.

[0611] Specific examples of polyoxyethylene alkyl phenyl ethers: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, etc.

[0612] Specific examples of polyoxyethylene alkyl esters: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, etc.

[0613] Specific examples of sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.

[0614] Specific examples of polyoxyethylene sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, etc.

[0615] Specific examples of glycerol esters: glycerol monomyristate, glycerol monostearate, glycerol monooleate, etc.

[0616] Specific examples of the above derivatives: polyoxyethylene alkylamines, polyoxyethylene alkyl phenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, etc.

[0617] The above ethers and esters may have an HLB value of 10 to 18.

[0618] Examples of nonionic surfactants include the Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol (registered trademark) L series manufactured by Dow Chemical Company, the Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m~22, n~23)), Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10, etc.) manufactured by BASF Corporation.

[0619] The above nonionic surfactant itself provides polymerization sites, and then transfers radicals by chain transfer in the initial stage, thereby providing a large amount of low molecular weight fluoropolymers, which can thus become nucleation sites.

[0620] As the above nonionic surfactant, a fluorine-free nonionic surfactant is preferred. Examples include: ether-type nonionic surfactants such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers; polyoxyethylene derivatives such as ethylene oxide / propylene oxide block copolymers; ester-type nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters; amine-based nonionic surfactants such as polyoxyethylene alkyl amines, alkyl alkanolamides; etc.

[0621] In the above nonionic surfactant, the hydrophobic group can be any one of alkylphenyl groups, straight-chain alkyl groups, and branched-chain alkyl groups.

[0622] As the nonionic surfactant, a nonionic surfactant represented by the general formula (i) is preferred.

[0623] R 6 -O-A 1 -H (i)

[0624] (In the formula, R 6 is a straight-chain or branched-chain primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.)

[0625] In the general formula (i), the number of carbon atoms of R 6 is preferably 10 to 16, more preferably 12 to 16. If the number of carbon atoms of R 6 is 18 or less, excellent sedimentation stability of the composition is easily obtained. In addition, if the number of carbon atoms of R 6 exceeds 18, the flow temperature is high, so it is difficult to handle. If R 6If the number of carbon atoms is less than 8, the surface tension of the composition increases, and the permeability and wettability are likely to decrease.

[0626] The polyoxyalkylene chain may be composed of ethylene oxide and propylene oxide. It is a polyoxyalkylene chain composed of an average repeating number of 5 - 20 of ethylene oxide groups and an average repeating number of 0 - 2 of propylene oxide groups, and is a hydrophilic group. The number of ethylene oxide units may include either a normally provided broad or narrow unimodal distribution, or a broader or bimodal distribution obtained by blending. When the average repeating number of propylene oxide groups exceeds 0, the ethylene oxide groups and propylene oxide groups in the polyoxyalkylene chain may be arranged in a block form or in a random form. From the aspects of the viscosity and sedimentation stability of the composition, a polyoxyalkylene chain composed of an average repeating number of 7 - 12 of ethylene oxide groups and an average repeating number of 0 - 2 of propylene oxide groups is preferred. In particular, if A 1 has an average of 0.5 - 1.5 propylene oxide groups, it has good low foaming property, so it is preferred.

[0627] More preferably, R 6 is (R’)(R”)HC-, where R’ and R” are the same or different straight-chain, branched-chain or cyclic alkyl groups, and the total number of carbon atoms is at least 5, preferably 7 - 17. It is preferred that at least one of R’ or R” is a branched or cyclic hydrocarbon group.

[0628] As a specific example of the above polyoxyethylene alkyl ether, C 13 H 27 -O-(C2H4O) 10 -H, C 12 H 25 -O-(C2H4O) 10 -H, C 10 H 21 CH(CH3)CH2-O-(C2H4O)9-H, C 13 H 27 -O-(C2H4O)9-(CH(CH3)CH2O)-H, C 16 H 33 -O-(C2H4O) 10 -H, HC(C5H 11 )(C7H 15)-O-(C2H4O)9-H and the like. As commercially available products of the above polyoxyethylene alkyl ethers, for example, Genapol X080 (product name, manufactured by Clariant), the Noigen TDS series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) typified by Noigen TDS-80 (trade name), the Leocol TD series (manufactured by LION Corporation) typified by Leocol TD-90 (trade name), the LIONOL (registered trademark) TD series (manufactured by LION Corporation), the T-Det A series (manufactured by Harcros Chemicals) typified by T-Det A138 (trade name), the TERGITOL (registered trademark) 15S series (manufactured by The Dow Chemical Company), etc. can be mentioned.

[0629] The above nonionic surfactant is also preferably an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 4 to about 18 ethylene oxide units, an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 6 to about 12 ethylene oxide units, or a mixture thereof. Nonionic surfactants of this type are also commercially available, for example, as TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (all product names, manufactured by The Dow Chemical Company).

[0630] In addition, the hydrophobic group of the nonionic surfactant can be any of an alkylphenyl group, a straight-chain alkyl group, and a branched-chain alkyl group. For example, as the nonionic surfactant, for example, the general formula (ii)

[0631] R 7 -C6H4-O-A 2 -H (ii)

[0632] (wherein R 7 is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms, and A 2 is a polyoxyalkylene chain) represented nonionic surfactant. As the above nonionic surfactant, specifically, TRITON X-100 (trade name, manufactured by The Dow Chemical Company), etc. can be mentioned.

[0633] As the above nonionic surfactant, polyol compounds can also be mentioned. Specifically, polyol compounds described in International Publication No. 2011 / 014715 etc. can be mentioned. As typical examples of polyol compounds, compounds having one or more sugar units as polyol units can be mentioned. The sugar unit can be modified to contain at least one long chain. As suitable polyol compounds containing at least one long chain portion, for example, alkyl glycosides, modified alkyl glycosides, sugar esters, and combinations thereof can be mentioned. As sugars, monosaccharides, oligosaccharides, and sorbitans can be mentioned, but are not limited thereto. As monosaccharides, pentoses and hexoses can be mentioned. As typical examples of monosaccharides, ribose, glucose, galactose, mannose, fructose, arabinose, and xylose can be mentioned. As oligosaccharides, oligomers of 2 to 10 identical or different monosaccharides can be mentioned. As examples of oligosaccharides, sucrose, maltose, lactose, raffinose, and isomaltose can be mentioned, but are not limited thereto.

[0634] Typically, as sugars suitable for use as polyol compounds, cyclic compounds of a five-membered ring containing 4 carbon atoms and 1 heteroatom (typically oxygen or sulfur, preferably an oxygen atom), or cyclic compounds of a six-membered ring containing 5 carbon atoms and the above 1 heteroatom, preferably an oxygen atom, can be mentioned. They further contain at least 2 or at least 3 hydroxyl groups (-OH groups) bonded to the carbocyclic atoms. Typically, in order to form an ether or ester bond between the long chain residue and the sugar moiety, the sugar is modified in the following aspect: one or more of the hydrogen atoms of the hydroxyl group (and / or hydroxyalkyl group) bonded to the carbocyclic atoms are replaced by long chain residues. The sugar-based polyol can contain one sugar unit or two or more sugar units. One sugar unit or two or more sugar units can be modified with the above long chain portion. As specific examples of sugar-based polyol compounds, glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof can be mentioned.

[0635] Preferred types of polyol compounds are alkyl or modified alkyl glycosides. These types of surfactants contain at least one glucose moiety. There can be mentioned

[0636]

Chemical formula 24

[0637]

[0638] (In the formula, x represents 0, 1, 2, 3, 4, or 5, R 1 and R 2 independently represent H or a long chain unit containing at least 6 carbon atoms, where at least one of R 1 and R 2 is not H) the compound shown. As R 1 and R 2A typical example of which is an aliphatic alcohol residue. Examples of aliphatic alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof. The above formula shows a specific example of an alkyl polyglycoside of glucose in the pyranose form, but it is understood that other sugars or sugars of the same type but in different enantiomeric or diastereomeric forms can also be used.

[0639] Alkyl glycosides can be obtained, for example, by the acid-catalyzed reaction of glucose, starch, or n-butyl glycoside with an aliphatic alcohol. In a typical example, a mixture of various alkyl glycosides is obtained thereby (Alkylpolygylcoside, Rompp, Lexikon Chemie, Version 2.0, Stuttgart / New York, Georg Thieme Verlag, 1999). Examples of aliphatic alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof. In addition, alkyl glycosides are commercially available under the trade names GLUCOPON or DISPONIL from Cognis GmbH, Düsseldorf, Germany.

[0640] As other nonionic surfactants, there are bifunctional block copolymers supplied by BASF as Pluronic (registered trademark) R series and tridecanol alkoxylates supplied by BASF Corporation as Iconol (registered trademark) TDA series.

[0641] As the above nonionic surfactant, it is preferably at least one selected from the group consisting of the nonionic surfactant represented by the general formula (i) and the nonionic surfactant represented by the general formula (ii), and more preferably the nonionic surfactant represented by the general formula (i).

[0642] As the above nonionic surfactant, it is preferably free of an aromatic moiety.

[0643] Regarding the content of the nonionic surfactant in the composition, relative to PTFE, it can be 1.0% by mass or more, preferably 1.5% by mass or more, more preferably 2.0% by mass or more, further preferably 2.5% by mass or more, particularly preferably 3.0% by mass or more, and most preferably 4.0% by mass or more. In addition, regarding the content of the nonionic surfactant in the composition, relative to PTFE, it is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 12% by mass or less.

[0644] <aqueous medium>

[0645] The composition of the present invention contains an aqueous medium. The aqueous medium refers to a liquid containing water. The above-mentioned aqueous medium is not particularly limited as long as it contains water, and may contain water and a non-fluorinated organic solvent such as an alcohol, an ether, a ketone, etc. and / or a fluorinated organic solvent having a boiling point of 40°C or lower.

[0646] <anionic hydrocarbon surfactant>

[0647] In one embodiment of the composition of the present invention, an anionic hydrocarbon surfactant is contained. By using an anionic hydrocarbon surfactant, it is possible to appropriately adjust the viscosity of the composition or improve the miscibility of pigments, fillers, etc. while maintaining the excellent sedimentation stability of the composition.

[0648] In another embodiment of the composition of the present invention, it substantially does not contain an anionic hydrocarbon surfactant. The composition of the present invention has excellent sedimentation stability even when it substantially does not contain an anionic hydrocarbon surfactant.

[0649] In the present invention, "substantially does not contain an anionic hydrocarbon surfactant" means that the content of the anionic hydrocarbon surfactant in the composition is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and still more preferably 1 mass ppb or less.

[0650] An anionic hydrocarbon surfactant generally has a hydrophilic part such as a carboxylate, a sulfonate, or a sulfate, and a hydrophobic part such as an alkyl group as a long-chain hydrocarbon part.

[0651] Examples of the anionic hydrocarbon surfactant include Versatic (registered trademark) 10 of Resolution Performance Products, Avanel S series (S-70, S-74, etc.) manufactured by BASF Corporation, etc.

[0652] Examples of the anionic hydrocarbon surfactant also include those represented by R-L-M (wherein R is a linear or branched alkyl group having 1 or more carbon atoms with or without substituents or a cyclic alkyl group having 3 or more carbon atoms with or without substituents, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. L is -ArSO3 - 、-SO3 - 、-SO4-, -PO3 - or -COO - , and M is H, a metal atom, NR 54. An imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5 is H or an organic group, -ArSO3 - is an arylsulfonate) an anionic surfactant represented by.

[0653] Specifically, examples include those represented by lauric acid and lauryl sulfate, CH3-(CH2) n -L-M (where n is an integer from 6 to 17. L and M are the same as above). A mixture of substances where R is an alkyl group with 12 to 16 carbon atoms and L-M is a sulfate can also be used.

[0654] In addition, as an anionic hydrocarbon surfactant, examples also include those represented by R 6 (-L-M)2 (where R 6 is a linear or branched alkylene group with 1 or more carbon atoms with or without substituents, or a cyclic alkylene group with 3 or more carbon atoms with or without substituents. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle and may also form a ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - , and M is H, a metal atom, NR 5 4. An imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5 is H or an organic group, -ArSO3 - is an arylsulfonate) an anionic surfactant represented by.

[0655] In addition, as an anionic hydrocarbon surfactant, examples also include those represented by R 7 (-L-M)3 (where R 7 is a linear or branched alkylene group with 1 or more carbon atoms with or without substituents, or a cyclic alkylene group with 3 or more carbon atoms with or without substituents. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle and may also form a ring. L is -ArSO3 - , -SO3 - , -SO4 - , -PO3 - or -COO - , and M is H, a metal atom, NR 5 4. An imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5is H or an organic group. -ArSO3 - is an anionic surfactant represented by an arylsulfonate).

[0656] In addition, as an anionic hydrocarbon surfactant, a silicone hydrocarbon surfactant can also be cited. As the silicone hydrocarbon surfactant, substances described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104 can be cited. The structure of the silicone hydrocarbon surfactant contains a distinct hydrophobic part and a hydrophilic part. The hydrophobic part contains one or more dihydrocarbylsiloxane units, where the substituents on the silicon atom are entirely hydrocarbons. When the carbon atoms of the hydrocarbon group can be substituted by halogens such as fluorine, in the sense of being completely substituted by hydrogen atoms, these silicone surfactants can also be regarded as hydrocarbon surfactants, that is, the monovalent substituents on the carbon atoms of the hydrocarbon group are hydrogen.

[0657] The hydrophilic part of the silicone hydrocarbon surfactant can contain one or more polar parts containing ionic groups such as sulfate esters, sulfonate esters, phosphonate esters, phosphate esters, carboxylate esters, carbonate esters, sulfosuccinate esters, taurate esters (in the form of free acids, salts or esters), phosphine oxides, betaines, betaine polyols, quaternary ammonium salts, etc. The ionic hydrophobic part can also contain an ionically functionalized silicone graft. As such a silicone hydrocarbon surfactant, for example, polydimethylsiloxane-grafted-(meth)acrylate, polydimethylsiloxane-grafted-polyacrylate salt, and polydimethylsiloxane-grafted quaternary amine can be cited. The polar part of the hydrophilic part of the silicone hydrocarbon surfactant can contain: polyethers such as polyethylene oxide (PEO) and mixed polyethylene oxide / propylene oxide polyethers (PEO / PPO); monosaccharides and disaccharides; and nonionic groups formed by water-soluble heterocycles such as pyrrolidone. The ratio of ethylene oxide to propylene oxide (EO / PO) can vary in the mixed polyethylene oxide / propylene oxide polyether.

[0658] The hydrophilic part of the silicone hydrocarbon surfactant can also contain a combination of an ionic part and a nonionic part. As such a part, for example, a polyether or a polyol end-functionalized or randomly functionalized with an ionic group can be cited. Preferred for the implementation of the present invention is a silicone having a nonionic part, that is, a nonionic silicone surfactant.

[0659] The configuration of the hydrophobic and hydrophilic parts of the structure of the silicone hydrocarbon surfactant can take the form of a diblock polymer (AB), a triblock polymer (ABA) (here, "B" represents the silicone part of the molecule), or a multiblock polymer. Alternatively, the silicone surfactant can contain a graft polymer.

[0660] Regarding siloxane hydrocarbon surfactants, they are also disclosed in the specification of U.S. Patent No. 6,841,616.

[0661] As anionic hydrocarbon surfactants based on a siloxane matrix, examples include Noveon (registered trademark) of Lubrizol Advanced Materials, Inc., and SilSense available from Consumer Specialties TM PE - 100 Silicone, SilSense TM CA - 1 Silicone, etc.

[0662] As anionic hydrocarbon surfactants, examples also include sulfosuccinate surfactants such as Lankropol (registered trademark) K8300 of Akzo Nobel Surface Chemistry LLC. As sulfosuccinate surfactants, examples include sodium diisodecyl sulfosuccinate, (Emulsogen (registered trademark) SB10 of Clariant), sodium diisotridecyl sulfosuccinate (Polirol (registered trademark) TR / LNA of Cesapinia Chemicals), etc.

[0663] As anionic hydrocarbon surfactants, examples also include PolyFox (registered trademark) surfactants (PolyFox TM PF - 156A, PolyFox TM PF - 136A, etc.) of Omnova Solutions, Inc.

[0664] As anionic hydrocarbon surfactants, for example, those represented by the general formula (α):

[0665] R 10 -COOM (α)

[0666] (wherein, R 10 is a monovalent organic group containing one or more carbon atoms. M is H, a metal atom, NR 11 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 11 is H or an organic group, which may be the same or different) of the compound (α). As R 11 , H or a C 1-10 organic group is preferred, and H or a C 1-4 organic group is more preferred. From the aspect of surface activity ability, R 10The number of carbon atoms is preferably 2 or more, more preferably 3 or more. Further, from the aspect of water solubility, R 10 The number of carbon atoms is preferably 29 or less, more preferably 23 or less. Examples of the metal atom of M include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. As M, H, a metal atom, or NR 11 4 is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 11 4 is more preferred. Further, H, Na, K, Li, or NH4 is more preferred, and further, Na, K, or NH4 is more preferred, particularly Na or NH4 is preferred, and most preferably NH4.

[0667] Examples of the compound (α) also include those represented by R 12 -COOM (wherein R 12 is a linear or branched alkyl, alkenyl, alkylene, or alkenylene having 1 or more carbon atoms with or without substituents, or a cyclic alkyl, alkenyl, alkylene, or alkenylene having 3 or more carbon atoms with or without substituents, and they may contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle and may form a ring. M is the same as above) anionic surfactants. Specifically, those represented by CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28. M is the same as above) can be cited.

[0668] From the aspect of emulsion stability, the compound (α) may not contain a carbonyl group (excluding the carbonyl group in the carboxyl group). As the hydrocarbon-containing surfactant that does not contain a carbonyl group, for example, the following formula (A) is preferably exemplified:

[0669] R-COO-M (A)

[0670] (wherein R is an alkyl, alkenyl, alkylene, or alkenylene, and they may contain an ether bond. M is H, a metal atom, NR 11 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents. R 11 are the same or different and are H or an organic group having 1 to 10 carbon atoms) compounds. In the above formula (A), R is preferably an alkyl or alkenyl (they may contain an ether group). The alkyl or alkenyl in the above R may be linear or branched. The number of carbon atoms of the above R is not limited, for example, it is 2 to 29.

[0671] When the alkyl group is linear, the number of carbon atoms of R is preferably 3 to 29, more preferably 5 to 23. When the above alkyl group is branched, the number of carbon atoms of R is preferably 5 to 35, more preferably 11 to 23. When the above alkenyl group is linear, the number of carbon atoms of R is preferably 2 to 29, more preferably 9 to 23. When the above alkenyl group is branched, the number of carbon atoms of R is preferably 2 to 29, more preferably 9 to 23.

[0672] Examples of the alkyl group and the alkenyl group include methyl, ethyl, isobutyl, tert-butyl, vinyl, and the like.

[0673] In addition, as the anionic hydrocarbon surfactant, a carboxylic acid type hydrocarbon surfactant can also be cited. Examples of the carboxylic acid type hydrocarbon surfactant include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, isoleic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12) linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, palmitoleic acid, cis-6-hexadecenoic acid, oleic acid, elaidic acid, isoleic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-elaidic acid, β-elaidic acid, eicosatrienoic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, octadecatetraenoic acid, arachidonic acid, eicosatetraenoic acid, docosatetraenoic acid, eicosapentaenoic acid, docosapentaenoic acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, herring acid, and salts thereof. At least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof is particularly preferred. Examples of the above salts include salts in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 11 4, salts of imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents are not particularly limited.

[0674] In addition, as the anionic hydrocarbon surfactant, for example, the anionic hydrocarbon surfactants described in International Publication No. 2013 / 146950 and International Publication No. 2013 / 146947 can be used. Examples include anionic hydrocarbon surfactants having a saturated or unsaturated aliphatic chain with 6 to 40 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 9 to 13 carbon atoms. The above saturated or unsaturated aliphatic chain can be either linear or branched and can also have a cyclic structure. The above hydrocarbon can be aromatic or can have an aromatic group. The above hydrocarbon can also have heteroatoms such as oxygen, nitrogen, and sulfur.

[0675] Examples of the anionic hydrocarbon surfactant include alkyl sulfonates, alkyl sulfates, alkyl aryl sulfates and their salts; aliphatic (carboxylic) acids and their salts; alkyl phosphate esters, alkyl aryl phosphate esters or their salts; etc. Among them, alkyl sulfonates, alkyl sulfates, aliphatic carboxylic acids or their salts are preferred.

[0676] As the alkyl sulfate or its salt, ammonium lauryl sulfate and sodium lauryl sulfate are preferred.

[0677] As the aliphatic carboxylic acid or its salt, succinic acid, capric acid, undecanoic acid, undecylenic acid, lauric acid, hydrogenated lauric acid or their salts are preferred.

[0678] Regarding the content of the anionic hydrocarbon surfactant in the composition, relative to PTFE, it is preferably 10 mass ppm to 5000 mass ppm, more preferably 50 mass ppm to 5000 mass ppm, further preferably 50 mass ppm to 3000 mass ppm, and particularly preferably 50 mass ppm to 2000 mass ppm. By making the content of the anionic hydrocarbon surfactant within the above range, the viscosity of the composition can be appropriately adjusted, or the miscibility of pigments, fillers, etc. can be improved.

[0679] <Other components>

[0680] The composition of the present invention may also contain other components. Examples of other components include preservatives. By making the composition contain a preservative, even when the composition is stored for a long time, the corruption of the composition and the propagation of bacteria can be inhibited in a state where the sedimentation of PTFE is suppressed.

[0681] Examples of the preservative include isothiazolone-based, oxazole-based, bronopol, chlorothalonil, methylsulfonyl tetrachloropyridine, carbendazim, 2-[(dichlorofluoromethyl)-thio]-1H-isoindole-1,3-(2H)-dione (Fluor Folpet), sodium diacetate, diiodomethyl p-tolyl sulfone, etc.

[0682] Regarding the content of the preservative in the composition, relative to PTFE, it is preferably 0.01 mass% to 0.5 mass%, more preferably 0.05 mass% to 0.2 mass%.

[0683] In addition, as other components, water-soluble high molecular compounds can be cited. Examples of the water-soluble high molecular compounds include methylcellulose, alumina sol, polyvinyl alcohol, carboxylated vinyl polymer, polyethylene oxide (dispersion stabilizer), polyethylene glycol (dispersion stabilizer), polyvinylpyrrolidone (dispersion stabilizer), phenolic resin, urea resin, epoxy resin, melamine resin, polyester resin, polyether resin, acrylic organosilicon resin, organosilicon resin, silicone polyester resin, polyurethane resin, and the like.

[0684] <Fluorine-containing surfactant>

[0685] In one embodiment of the composition of the present invention, a fluorine-containing surfactant is contained. By using the fluorine-containing surfactant, it is possible to appropriately adjust the viscosity of the composition or improve the miscibility of pigments, fillers, etc. while maintaining the excellent sedimentation stability of the composition.

[0686] In another embodiment of the composition of the present invention, the fluorine-containing surfactant is substantially not contained. Even when the fluorine-containing surfactant is substantially not contained in the composition of the present invention, the sedimentation stability is excellent.

[0687] In the present invention, "substantially not containing a fluorine-containing surfactant" means that the content of the fluorine-containing surfactant in the composition is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably the fluorine-containing surfactant obtained by measurement based on liquid chromatography-mass spectrometry (LC / MS / MS) is below the detection limit.

[0688] In another embodiment of the composition of the present invention, the anionic fluorine-containing surfactant is substantially not contained. Even when the anionic fluorine-containing surfactant is substantially not contained in the composition of the present invention, the sedimentation stability is excellent.

[0689] In the present invention, "substantially not containing an anionic fluorine-containing surfactant" means that the content of the anionic fluorine-containing surfactant in the composition is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably the detection limit obtained by measurement based on liquid chromatography-mass spectrometry (LC / MS / MS) is below the detection limit.

[0690] In another embodiment of the composition of the present invention, a fluorine-containing anionic surfactant having an anionic moiety with a molecular weight of 800 or less is substantially not contained. Even when the composition of the present invention substantially does not contain a fluorine-containing anionic surfactant having an anionic moiety with a molecular weight of 800 or less, the sedimentation stability is excellent.

[0691] In the present invention, "substantially not containing a fluorine-containing anionic surfactant having an anionic moiety with a molecular weight of 800 or less" means that the content of the fluorine-containing anionic surfactant having an anionic moiety with a molecular weight of 800 or less in the composition is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably below the detection limit obtained by measurement based on liquid chromatography-mass spectrometry (LC / MS / MS).

[0692] The content of the fluorosurfactant can be quantified by a known method. For example, quantification can be performed by LC / MS / MS analysis. First, the composition is extracted into an organic solvent of methanol, and molecular weight information is selected from the LC / MS / MS spectrum of the extract, and it is confirmed that it is consistent with the structural formula of the surfactant as a candidate.

[0693] Thereafter, aqueous solutions having 5 or more concentration levels are prepared for the confirmed surfactant, LC / MS / MS analysis is performed for each concentration, and a calibration curve with respect to the area of the region is prepared.

[0694] The Soxhlet extraction of the composition with methanol and the LC / MS / MS analysis of the extract enable quantitative determination.

[0695] That is, the content of the fluorosurfactant can be measured, for example, by adding methanol to the composition, performing extraction, and performing LC / MS / MS analysis on the obtained extract.

[0696] In order to further improve the extraction efficiency, treatment such as Soxhlet extraction and ultrasonic treatment can be performed.

[0697] Molecular weight information is selected from the obtained LC / MS / MS spectrum, and it is confirmed that it is consistent with the structural formula of the candidate fluorosurfactant.

[0698] Thereafter, aqueous solutions having 5 or more content levels are prepared for the confirmed fluorosurfactant, LC / MS / MS analysis is performed for each aqueous solution of the content, and a graph is made of the relationship between the content and the area of the region with respect to the content, and a calibration curve is plotted.

[0699] Then, using the calibration curve, the area of the LC / MS / MS chromatogram region of the fluorosurfactant in the extract can be converted into the content of the fluorosurfactant.

[0700] Examples of the fluorosurfactant include anionic fluorosurfactants. The anionic fluorosurfactant can be, for example, a surfactant containing fluorine atoms with a total carbon atom number of 20 or less in the part other than the anionic group.

[0701] In addition, the fluorosurfactant can also be a fluorine-containing surfactant with a molecular weight of the anionic part of 800 or less. It should be noted that the above "anionic part" refers to the part of the above fluorosurfactant other than the cation. For example, in the case of F(CF2) n1 COOM shown in the following formula (I), it is the part of "F(CF2) n1 COO".

[0702] In addition, examples of the above fluorosurfactant include fluorosurfactants with a LogPOW of 3.5 or less. The above LogPOW is the partition coefficient of 1-octanol and water, which is represented by LogP [where P represents the ratio of the concentration of the fluorosurfactant in octanol to the concentration of the fluorosurfactant in water when the octanol / water (1:1) mixed solution containing the fluorosurfactant undergoes phase separation]. The above LogPOW is calculated as follows: Under the conditions of column: TOSOH ODS-120T column ( manufactured by Tosoh Corporation), eluent: acetonitrile / 0.6 mass% HClO4 water = 1 / 1 (vol / vol%), flow rate: 1.0 ml / minute, sample volume: 300 μL, column temperature: 40 °C, detection light: UV210 nm, HPLC is performed on standard substances (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) with known octanol / water partition coefficients to prepare a calibration curve of each elution time and the known octanol / water partition coefficient. Based on this calibration curve, it is calculated from the elution time of HPLC in the sample solution.

[0703] Specific examples of the fluorinated surfactant include U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 142541, U.S. Patent Application Publication No. 2008 / 0015319, and U.S. Patent No. 3250808. The fluorinated surfactants described in the patent application document, U.S. Patent No. 3,271,341, Japanese Patent Application Publication 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, and International Publication No. 2013 / 189826, etc.

[0704] Examples of the anionic fluorinated surfactant include those of the general formula (N 0 ):

[0705] X n0 -Rf n0 -Y 0 (N 0 )

[0706] (Where X n0 is H, Cl or and F. Rf n0 It is a chain, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H groups are replaced by F. The alkylene group may contain one or more ether bonds, and some of the H groups may be replaced by Cl. 0 is an anionic group).

[0707] Y 0 The anionic group may be -COOM, -SO2M or -SO3M, or -COOM or -SO3M. M is H, a metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K or Li. 7 , can be H or C 1-10The organic group can also be H or C 1-4 The organic group can also be H or C 1-4 The alkyl group. M can be H, a metal atom or NR 7 4, or it can also be H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4, or it can also be H, Na, K, Li or NH4. In the above Rf n0 , more than 50% of H can be substituted by fluorine.

[0708] As the compound represented by the general formula (N 0 ), the following can be cited:

[0709] General formula (N 1 ):

[0710] X n0 -(CF2) m1 -Y 0 (N 1 )

[0711] (In the formula, X n0 is H, Cl and F, m1 is an integer from 3 to 15, and Y 0 is the substance defined above) the represented compound; General formula (N 2 ):

[0712] Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 )

[0713] (In the formula, Rf n1 is a perfluoroalkyl group with 1 to 5 carbon atoms, m2 is an integer from 0 to 3, X n1 is F or CF3, and Y 0 is the substance defined above) the represented compound; General formula (N 3 ):

[0714] Rf n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 )

[0715] (In the formula, Rf n2 is a partially or fully fluorinated alkyl group with 1 to 13 carbon atoms that may contain an ether bond, m3 is an integer from 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group with 1 to 3 carbon atoms, q is 0 or 1, and Y 0A compound represented by the above-defined substance); general formula (N 4 ):

[0716] Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 )

[0717] (In the formula, Rf n4 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and may contain an ether bond and / or a chlorine atom, Y n1 and Y n2 are the same or different and are H or F, p is 0 or 1, and Y 0 is a compound represented by the above-defined substance); general formula (N 5 ):

[0718]

Chemical formula 25

[0719]

[0720] (In the formula, X n2 , X n3 and X n4 may be the same or different and are H, F, or a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and may contain an ether bond. Rf 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 linking group, and Y 0 is a substance as defined above. Among them, X n2 , X n3 , X n4 and Rf n5 have a total carbon atom count of 18 or less) and the like.

[0721] As the general formula (N 0The compounds shown, more specifically, examples include perfluorocarboxylic acids (I) represented by general formula (I), ω-H perfluorocarboxylic acids (II) represented by general formula (II), perfluoropolyether carboxylic acids (III) represented by general formula (III), perfluoroalkylalkylene carboxylic acids (IV) represented by general formula (IV), perfluoroalkoxyfluorocarboxylic acids (V) represented by general formula (V), perfluoroalkylsulfonic acids (VI) represented by general formula (VI), ω-H perfluoroalkylsulfonic acids (VII) represented by general formula (VII), perfluoroalkylalkylene sulfonic acids (VIII) represented by general formula (VIII), alkylalkylene carboxylic acids (IX) represented by general formula (IX), fluorocarboxylic acids (X) represented by general formula (X), alkoxyfluorosulfonic acids (XI) represented by general formula (XI), compounds (XII) represented by general formula (XII), compounds (XIII) represented by the following general formula (XIII), and the like.

[0722] The above perfluorocarboxylic acid (I) is represented by general formula (I):

[0723] F(CF2) n1 COOM (I)

[0724] (In the formula, n1 is an integer from 3 to 14, and M is H, a metal atom, NR 7 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 7 is H or an organic group).

[0725] The above ω-H perfluorocarboxylic acid (II) is represented by general formula (II):

[0726] H(CF2) n2 COOM (II)

[0727] (In the formula, n2 is an integer from 4 to 15, and M is the substance defined above).

[0728] The above perfluoropolyether carboxylic acid (III) is represented by general formula (III):

[0729] Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III)

[0730] (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is the substance defined above).

[0731] The above perfluoroalkylalkylene carboxylic acid (IV) is represented by general formula (IV):

[0732] Rf 2 (CH2)n4 Rf 3 COOM (IV)

[0733] (wherein, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a perfluoroalkylene group having 1 to 3 carbon atoms which is linear or branched, n4 is an integer of 1 to 3, and M is the substance defined above).

[0734] The above alkoxyfluorocarboxylic acid (V) is represented by the general formula (V):

[0735] Rf 4 -O-CY 1 Y 2 CF2-COOM (V)

[0736] (wherein, Rf 4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond and / or a chlorine atom, Y 1 and Y 2 are the same or different and are H or F, and M is the substance defined above).

[0737] The above perfluoroalkylsulfonic acid (VI) is represented by the general formula (VI):

[0738] F(CF2) n5 SO3M (VI)

[0739] (wherein, n5 is an integer of 3 to 14, and M is the substance defined above).

[0740] The above ω-H perfluoroalkylsulfonic acid (VII) is represented by the general formula (VII):

[0741] H(CF2) n6 SO3M (VII)

[0742] (wherein, n6 is an integer of 4 to 14, and M is the substance defined above).

[0743] The above perfluoroalkylalkylene sulfonic acid (VIII) is represented by the general formula (VIII):

[0744] Rf 5 (CH2) n7 SO3M (VIII)

[0745] (wherein, Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is the substance defined above).

[0746] The above alkylalkylene carboxylic acid (IX) is represented by the general formula (IX):

[0747] Rf 6 (CH2) n8 COOM (IX)

[0748] (wherein, Rf 6 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 13 carbon atoms and may contain an ether bond, n8 is an integer of 1 to 3, and M is as defined above).

[0749] The above-mentioned fluoro carboxylic acid (X) is represented by the general formula (X):

[0750] Rf 7 -O-Rf 8 -O-CF2-COOM (X)

[0751] (wherein, Rf 7 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and may contain an ether bond and / or a chlorine atom, Rf 8 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above).

[0752] The above-mentioned alkoxy fluorosulfonic acid (XI) is represented by the general formula (XI):

[0753] Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI)

[0754] (wherein, Rf 9 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and may contain an ether bond and may contain chlorine, Y 1 and Y 2 are the same or different and are H or F, and M is as defined above).

[0755] The above-mentioned compound (XII) is represented by the general formula (XII):

[0756]

Chemical 26

[0757]

[0758] (wherein, X 1 , X 2 and X 3 may be the same or different and are H, F, and a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and may contain an ether bond, Rf 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, Y 0is represented by an anionic group). Y 0 may be -COOM, -SO2M or -SO3M, or may be -SO3M or COOM (wherein M is the substance defined above). As L, for example, a single bond, a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms and containing an ether bond can be cited.

[0759] The above compound (XIII) is represented by the following general formula (XIII):

[0760] Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM (XIII)

[0761] (wherein Rf 11 is a fluoroalkyl group having 1 to 5 carbon atoms containing chlorine, n9 is an integer from 0 to 3, n10 is an integer from 0 to 3, and M is the substance defined above). As the compound (XIII), CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10 CF2COONH4 (a mixture with an average molecular weight of 750, wherein n9 and n10 are the numbers defined above).

[0762] Thus, as the above anionic fluorosurfactant, carboxylic acid surfactants, sulfonic acid surfactants, etc. can be cited.

[0763] The fluorosurfactant may be one fluorosurfactant or a mixture containing two or more fluorosurfactants.

[0764] As the fluorosurfactant, compounds represented by the following formula can be cited. The fluorosurfactant may also be a mixture of these compounds. In one embodiment of the composition of the present invention, the compound represented by the following formula is substantially not contained.

[0765] F(CF2)7COOM,

[0766] F(CF2)5COOM,

[0767] H(CF2)6COOM,

[0768] CF3O(CF2)3OCHFCF2COOM,

[0769] C3F7OCF(CF3)CF2OCF(CF3)COOM,

[0770] CF3CF2CF2OCF(CF3)COOM,

[0771] CF3CF2OCF2CF2OCF2COOM,

[0772] C2F5OCF(CF3)CF2OCF(CF3)COOM,

[0773] CF3OCF(CF3)CF2OCF(CF3)COOM,

[0774] CF2ClCF2CF2OCF(CF3)CF2OCF2COOM,

[0775] CF2ClCF2CF2OCF2CF(CF3)OCF2COOM,

[0776] CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM,

[0777] CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM,

[0778]

Chemical 27

[0779]

[0780] (In each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents.)

[0781] In the present invention, "substantially not containing the compound represented by the above formula" means that the total content of the compound represented by the above formula in the composition is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, still more preferably 1 mass ppb or less, and particularly preferably below the detection limit obtained by measurement based on liquid chromatography - mass spectrometry (LC / MS / MS).

[0782] The composition of the present invention can be used as an aqueous coating composition by mixing known pigments, thickeners, dispersants, defoamers, antifreezing agents, film - forming aids and other compounding agents, or further compounding with other polymer compounds.

[0783] In addition, the composition of the present invention can be used as an additive for uses such as a binder for suppressing the shedding of active substances of an electrode, a binder use, a dripping - preventing agent and other compound uses, and a dust - suppression treatment use for preventing the flying of sand, dust, etc.

[0784] In addition, by coating a substrate made of metal or ceramic with the composition of the present invention, a coating film surface excellent in non-adhesiveness, low coefficient of friction, gloss, smoothness, abrasion resistance, weather resistance, and heat resistance can be formed, which is suitable for coating of rollers or cooking devices, impregnation processing of glass cloth, etc.

[0785] An organic sol of PTFE can also be prepared from the composition of the present invention. The above organic sol may contain PTFE and an organic solvent. Examples of the above organic solvent include ether solvents, ketone solvents, alcohol solvents, amide solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogenated hydrocarbon solvents. N-methyl-2-pyrrolidone, dimethylacetamide, etc. can be appropriately used. The preparation of the above organic sol can be carried out, for example, by the method described in International Publication No. 2012 / 002038.

[0786] Fine powder can be produced by precipitating the composition of the present invention. The composition of the present invention can be used in the form of fine powder for various uses after precipitation, washing, and drying. When precipitating the composition of the present invention, generally, the polymerization dispersion obtained by polymerization is diluted with water to a PTFE concentration of 5% by mass to 20% by mass, and if necessary, after adjusting the pH to neutral or alkaline, stirring is carried out more vigorously in a container with a stirrer than during the reaction. In the above precipitation, water-soluble organic compounds such as methanol and acetone, inorganic salts such as potassium nitrate and ammonium carbonate, or inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid can be added as precipitating agents and stirred simultaneously. In addition, the above precipitation can also be carried out continuously using a pipe mixer or the like.

[0787] From the aspect of productivity, the concentration of uncoagulated PTFE in the wastewater generated by the above coagulation is preferably low, more preferably less than 0.4% by mass, and particularly preferably less than 0.3% by mass.

[0788] Before or during the above precipitation, by adding a pigment for coloring or various fillers for improving mechanical properties, a pigment-containing or filler-containing PTFE fine powder uniformly mixed with the pigment or filler can be obtained.

[0789] The drying of the wet powder obtained by precipitating the composition of the present invention is usually carried out using means such as vacuum, high frequency, and hot air while maintaining a state where the above wet powder hardly flows, preferably in a static state. Friction between powders, especially at high temperatures, usually has an adverse effect on fine powder-type TFE polymers. This is because the particles composed of PTFE have the property of simply fibrillating even under a small shear force and losing the originally stable particle structure state.

[0790] The above drying can be carried out at a drying temperature of 10°C to 300°C, preferably 100°C to 300°C (preferably 100°C to 250°C).

[0791] The obtained PTFE fine powder is preferably used for molding. Suitable uses include tubes in hydraulic systems and fuel systems of aircraft and automobiles, etc., flexible hoses for reagents, vapors, etc., wire coating uses, etc.

[0792] The composition or PTFE fine powder of the present invention is also preferably used as a processing aid. When used as a processing aid, by mixing the composition or PTFE fine powder of the present invention in a matrix polymer, etc., the melt strength during the melt processing of the matrix polymer can be improved, and the mechanical strength, electrical properties, flame retardancy, anti-dripping property during combustion, and sliding property of the obtained polymer can be improved.

[0793] The composition or PTFE fine powder of the present invention is also preferably used as a battery binder and for dust-proof purposes.

[0794] The composition or PTFE fine powder of the present invention is also preferably used as a processing aid after being compounded with a resin other than PTFE. The composition or PTFE fine powder of the present invention is suitable as a raw material for PTFE described in, for example, Japanese Patent Laid-Open No. 11-49912, U.S. Patent No. 5804654, Japanese Patent Laid-Open No. 11-29679, and Japanese Patent Laid-Open No. 2003-2980. The processing aid using the composition or PTFE fine powder of the present invention is also not inferior to the processing aids described in the above-mentioned various publications.

[0795] The composition of the present invention is also preferably made into a co-precipitation powder by mixing with an aqueous dispersion of a melt-processable fluororesin and causing precipitation. The above co-precipitation powder is suitable as a processing aid.

[0796] Examples of the above melt-processable fluororesin include TFE / HFP copolymer (FEP), TFE / PAVE copolymer (PFA), ethylene / TFE copolymer (ETFE), ethylene / TFE / HFP copolymer (EFEP), etc., and FEP is preferred.

[0797] The non-fluororesin to which the above co-precipitation powder is added can be in powder form, granular form, or emulsion form. From the aspect of fully mixing each resin, it is preferred to perform the above addition while applying a shearing force by a known method such as extrusion kneading or roll kneading.

[0798] The composition of the present invention also preferably contains the above-mentioned melt-processable fluororesin. Examples of the above-mentioned melt-processable fluororesin include FEP, PFA, ETFE, EFEP, etc. The above-mentioned aqueous dispersion containing the above-mentioned melt-processable fluororesin can be used as a coating. The above-mentioned melt-processable fluororesin can sufficiently weld the particles of the above-mentioned TFE polymer to each other, thereby improving the film-forming property and making the obtained coating film shiny.

[0799] In addition, examples of the use of the composition of the present invention include: a coating formed by coating on a substrate and firing as needed after drying; an infiltration formed by infiltrating into a porous support such as a non-woven fabric or a resin molded product and preferably firing after drying; a casting film formed by coating on a substrate such as glass, drying, and then impregnating in water as needed and peeling off the substrate to obtain a film. Examples of these applications include an aqueous dispersion-type coating, a tent film, a conveyor belt, a printed circuit board (CCL), a bonding agent for electrodes, a waterproof agent for electrodes, etc.

[0800] The composition of the present invention is also preferably used as a dust suppression treatment agent. The above-mentioned dust suppression treatment agent can be used in the following methods: a method of mixing with a dust-generating substance and applying a compression-shear action to the mixture at a temperature of 20°C to 200°C to fibrillate the TFE polymer and thereby suppress the dust of the dust-generating substance; for example, the methods described in Japanese Patent No. 2827152, Japanese Patent No. 2538783, etc. The composition of the present invention can be suitably used in, for example, the dust suppression treatment agent composition described in International Publication No. 2007 / 004250, and can also be suitably used in the dust suppression treatment method described in International Publication No. 2007 / 000812.

[0801] The above-mentioned dust suppression treatment agent is suitable for dust suppression treatment in the fields of building materials, soil stabilization materials, solidifying materials, fertilizers, landfill treatment of incineration ash and harmful substances, explosion protection, cosmetics, and sands for pet excrement represented by cat litter.

[0802] The composition of the present invention is also preferably used as a raw material for obtaining TFE polymer fibers by the dispersion spinning method. The above-mentioned dispersion spinning method refers to the following method: mixing the composition of the present invention with an aqueous dispersion of a matrix polymer, extruding the mixture to form an intermediate fiber structure, and firing the intermediate fiber structure to decompose the above-mentioned matrix polymer and sinter the TFE polymer particles to obtain TFE polymer fibers.

[0803] In addition, when the PTFE contained in the composition of the present invention is high molecular weight PTFE, the high molecular weight PTFE powder obtained from the composition of the present invention has stretchability and non-melting processability, and is also useful as a raw material for stretch bodies (porous bodies). When the stretch body is a film (PTFE stretched film or PTFE porous film), stretching can be carried out by a known PTFE stretching method. By stretching, the high molecular weight PTFE is easily fibrillated to form a PTFE porous body (film) composed of nodules and fibers. It is preferable to perform roll stretching on a sheet-like or rod-like paste extrudate in the extrusion direction, whereby a uniaxially stretched film can be obtained. Furthermore, a biaxially stretched film can also be obtained by stretching in the width direction using a tenter or the like. It is also preferable to perform a semi-sintering treatment before stretching.

[0804] The PTFE stretch body is a porous body with a high porosity, and can be suitably used as a filter medium for various precision filters such as air filters and reagent filters, a support material for polymer electrolyte membranes, etc. In addition, it is also useful as a material for products used in the fields of fibers, medicine, electrochemistry, sealing materials, air filtration, ventilation / internal pressure adjustment, liquid filtration, general consumables, etc. Specific uses are exemplified below.

[0805] Electrochemistry field

[0806] Dielectric material prepregs, EMI shielding materials, heat transfer materials, etc. More specifically, printed circuit boards, electromagnetic shielding materials, insulating heat transfer materials, insulating materials, etc.

[0807] Sealing material field

[0808] Gaskets, seals, pump diaphragms, pump tubes, aircraft sealing materials, etc.

[0809] Air filtration field

[0810] 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 folded filters (for exhaust gas treatment), SINBRAN filters (for industrial use), catalytic filters (for exhaust gas treatment), filters with adsorbents (for HDD assembly), vent filters with adsorbents (for HDD assembly), vent filters (for HDD assembly, etc.), vacuum cleaner filters (for vacuum cleaners), general multi-layer felts, GT cartridge filters (for interchangeable products suitable for GT), cooling filters (for electronic equipment casings), etc.

[0811] Ventilation / internal pressure adjustment field

[0812] Freeze-drying materials for containers for freeze-drying, etc., automotive ventilation materials suitable for electronic circuits or lamps, container uses suitable for container lids, etc., protective ventilation uses suitable for electronic devices such as input board terminals or small terminals such as mobile phone terminals, medical ventilation uses, etc.

[0813] Liquid filtration field

[0814] Semiconductor liquid filters (for semiconductor manufacturing), hydrophilic PTFE filters (for semiconductor manufacturing), filters suitable for chemicals (for reagent treatment), filters for pure water production lines (for pure water production), backwash-type liquid filtration filters (for industrial wastewater treatment), etc.

[0815] General consumable materials field

[0816] Clothing, cable guide tubes (movable wires suitable for motorcycles), motorcycle clothing, casting pads (medical protective gear), vacuum cleaner filters, bagpipes (musical instruments), cables (signal cables for guitars, etc.), strings (for stringed instruments), etc.

[0817] Fiber field

[0818] PTFE fibers (fiber materials), sewing threads (for fabrics), knitting threads (for fabrics), ropes, etc.

[0819] Medical field

[0820] Implantable devices (stretched products), artificial blood vessels, catheters, general surgery (tissue reinforcement materials), head and neck products (dura mater substitutes), oral health (tissue regeneration medicine), orthopedics (bandages), etc.

[0821] In addition, when the PTFE contained in the composition of the present invention is low molecular weight PTFE, low molecular weight PTFE powder can also be obtained from the composition of the present invention. The low molecular weight powder can also be manufactured by subjecting the high molecular weight PTFE obtained from the composition of the present invention to low molecular weight conversion using a known method (thermal decomposition, radiation irradiation decomposition, etc.).

[0822] Low molecular weight PTFE with a molecular weight of 600,000 or less (also called PTFE micropowder) has excellent chemical stability, extremely low surface energy, and is not prone to fibrillation. Therefore, it is suitable as an additive for the manufacture of plastics, inks, cosmetics, coatings, greases, office automation equipment parts, toners, etc. for the purpose of improving sliding properties, texture of the coating film surface, etc. (for example, see Japanese Patent Laid-Open No. 10-147617).

[0823] In the present invention, high molecular weight PTFE refers to PTFE having non-melt processability and fibrillation property. Additionally, low molecular weight PTFE refers to PTFE having melt processability and no fibrillation property.

[0824] The above-mentioned non-melt processability refers to the 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.

[0825] The presence or absence of fibrillation property can be judged by "paste extrusion", which is a representative method for molding the powder made of the polymer of TFE, namely "high molecular weight PTFE powder". This is because, generally, when paste extrusion can be carried out, high molecular weight PTFE has fibrillation property. When the unfired molded product obtained by paste extrusion does not have substantial strength or elongation, for example, when the elongation is 0% and it will break if stretched, it can be regarded as having no fibrillation property.

[0826] The standard specific gravity (SSG) of the above-mentioned high molecular weight PTFE is preferably 2.130 to 2.280. The above-mentioned standard specific gravity is measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895-89. In the present invention, "high molecular weight" means that the above-mentioned standard specific gravity is within the above range.

[0827] The complex viscosity of the above-mentioned low molecular weight PTFE at 380 °C is 1×10 2 Pa·s to 7×10 5 Pa·s. In the present invention, "low molecular weight" means that the above-mentioned complex viscosity is within the above range.

[0828] The complex viscosity of the above-mentioned high molecular weight PTFE is significantly higher than that of the above-mentioned low molecular weight PTFE, and it is difficult to measure its accurate complex viscosity. On the other hand, the complex viscosity of the above-mentioned low molecular weight PTFE can be measured, but it is difficult to obtain a molded product for the measurement of standard specific gravity from the above-mentioned low molecular weight PTFE, and it is difficult to measure its accurate standard specific gravity. Therefore, in the present invention, the standard specific gravity is adopted as the index of the molecular weight of the above-mentioned high molecular weight PTFE, and the complex viscosity is adopted as the index of the molecular weight of the above-mentioned low molecular weight PTFE. It should be noted that for the above-mentioned high molecular weight PTFE and the above-mentioned low molecular weight PTFE, the measurement methods capable of directly specifying the molecular weight are unknown.

[0829] The peak temperature of the above-mentioned high molecular weight PTFE is preferably 333°C to 347°C, more preferably 335°C to 345°C. The peak temperature of the above-mentioned low molecular weight PTFE is preferably 322°C to 333°C, more preferably 324°C to 332°C. The above-mentioned peak temperature is the temperature corresponding to the maximum value in the following heat of fusion curve, and this heat of fusion curve is the heat of fusion curve when PTFE without a heating process above 300°C is heated at a rate of 10°C / minute using a differential scanning calorimeter [DSC]. In addition, the peak temperature can be determined as follows: Using TG / DTA (simultaneous differential thermal and thermogravimetric analyzer), PTFE without a heating process above 300°C is heated at a rate of 10°C / minute, and the temperature corresponding to the maximum value appearing in the differential thermal (DTA) curve thus obtained is specified as the peak temperature.

[0830] In the heat of fusion curve when PTFE without a heating process above 300°C is heated at a rate of 10°C / minute using a differential scanning calorimeter [DSC], the above-mentioned high molecular weight PTFE preferably shows at least one or more peaks in the range of 333°C to 347°C, and the heat of fusion in the range of 290°C to 350°C calculated from the above-mentioned heat of fusion curve is 62 mJ / mg or more.

[0831] An unfired tape (green tape) can also be obtained from PTFE fine powder.

[0832] Next, the manufacturing method of the present invention will be specifically described.

[0833] <Manufacturing Method of Composition>

[0834] The manufacturing method of the composition of the present invention includes the following steps: a step of polymerizing TFE in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), thereby obtaining a polymerization dispersion containing PTFE, polymer (I), and an aqueous medium; and a step of mixing the above-mentioned polymerization dispersion with a nonionic surfactant, thereby obtaining a composition containing PTFE, polymer (I), a nonionic surfactant, and an aqueous medium.

[0835] CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I)

[0836] (In the formula, X 1 and X 3 are each independently F, Cl, H, or CF3; X 2 is H, F, an alkyl group, or a fluoroalkyl group; A0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluoroalkyl group; m is an integer of 1 or more.)

[0837] By using the production method of the present invention, the above-described composition of the present invention can be easily produced.

[0838] The polymerization temperature and polymerization pressure during the polymerization of TFE are appropriately determined according to the type of monomer used, the molecular weight of the target PTFE, and the reaction rate. For example, the polymerization temperature is preferably 10°C to 150°C. The polymerization temperature is more preferably 30°C or higher, still more preferably 50°C or higher. Additionally, it is more preferably 120°C or lower, still more preferably 100°C or lower. The polymerization pressure is preferably 0.05 MPaG to 10 MPaG. The polymerization pressure is more preferably 0.3 MPaG or higher, still more preferably 0.5 MPaG or higher. Additionally, the polymerization pressure is more preferably 5.0 MPaG or lower, still more preferably 3.0 MPaG or lower.

[0839] The polymerization of TFE is carried out in the presence of polymer (I). As polymer (I), the substances as described above that are contained in the composition of the present invention and can also be appropriately used in the production method of the present invention can be used.

[0840] In the above polymerization, the amount of polymer (I) at the start of polymerization is preferably 1 mass ppm or more relative to the aqueous medium. The amount of polymer (I) at the start of polymerization is preferably 10 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 100 mass ppm or more, and even more preferably 200 mass ppm or more. There is no particular limitation on the upper limit. For example, it is preferably 100000 mass ppm, more preferably 50000 mass ppm. By making the amount of polymer (I) at the start of polymerization within the above range, a composition with more excellent sedimentation stability can be obtained.

[0841] The polymerization can be started when the gaseous fluoromonomer in the reactor becomes PTFE and the pressure in the reactor decreases. U.S. Patent No. 3,391,099 (Punderson) discloses a dispersion polymerization of TFE in an aqueous medium, which includes two different stages of the polymerization process. First is the formation of polymer nuclei as nucleation sites, and second is the growth stage of the polymerization including the established particles. It should be noted that the polymerization usually starts when both the monomer to be polymerized and the polymerization initiator are filled into the reactor. Additionally, in the present invention, an additive related to the formation of nucleation sites is used as a nucleating agent.

[0842] Polymer (I) is preferably added in an amount of 0.0001% by mass to 15% by mass relative to 100% by mass of the aqueous medium in terms of the total addition amount. A more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If it is less than 0.0001% by mass, the dispersing power may be insufficient, and if it exceeds 15% by mass, an effect commensurate with the addition amount cannot be obtained. The addition amount of polymer (I) is appropriately determined according to the type of monomer used, the molecular weight of the target PTFE, and the like.

[0843] The polymerization of TFE is carried out in an aqueous medium in the presence of polymer (I). In the polymerization of TFE, it is also preferable to continuously add polymer (I). The continuous addition of polymer (I) means, for example, adding polymer (I) not all at once but over time without interruption or in batches. By continuously adding polymer (I), a composition with more excellent sedimentation stability can be obtained.

[0844] In the case of continuously adding polymer (I), the addition amount of polymer (I) is preferably 0.001 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferable lower limit is 0.005% by mass, an even more preferable lower limit is 0.01% by mass, a more preferable upper limit is 5% by mass, and an even more preferable upper limit is 2% by mass.

[0845] In the production method of the present invention, it is also preferable to polymerize TFE with a modified monomer. By polymerizing TFE with a modified monomer, PTFE particles with small particle sizes can be obtained, and a composition with excellent sedimentation stability can be obtained.

[0846] The total amount of the modified monomer added during the polymerization of TFE is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, further preferably 0.001% by mass or more, and even more preferably 0.005% by mass or more relative to the obtained PTFE. In addition, the total amount of the modified monomer added during the polymerization is, in order of preference, 1.0% by mass or less, 0.90% by mass or less, 0.50% by mass or less, 0.40% by mass or less, 0.30% by mass or less, 0.20% by mass or less, 0.15% by mass or less, 0.10% by mass or less, 0.05% by mass or less relative to the obtained PTFE.

[0847] The manufacturing method of the present invention preferably further adds a modified monomer capable of copolymerizing with TFE before initiating the polymerization reaction, or before the polymerization reaction proceeds and the concentration of PTFE in the polymerization dispersion reaches 10.0% by mass, preferably before reaching 5.0% by mass. The modified monomer is usually added to the reaction vessel. By adding the modified monomer in the initial stage of polymerization, a composition with a small average primary particle size and excellent sedimentation stability can be obtained. The modified monomer can be added before the start of polymerization, or added simultaneously with the start of polymerization, as long as it is added after the start of polymerization and during the period of forming the nuclei of PTFE particles. The modified monomer may be added at least before the start of the polymerization reaction, or before the polymerization reaction proceeds and the concentration of PTFE in the polymerization dispersion reaches 10.0% by mass, and the modified monomer may be further added after the concentration of PTFE exceeds 10.0% by mass. For example, the modified monomer can be added before the concentration of PTFE reaches 10.0% by mass or less, and the addition of the modified monomer can be continued even if it exceeds 10.0% by mass. In addition, the modified monomer can be added at least once before the concentration of PTFE particles reaches 10.0% by mass, and at least once more after exceeding 10.0% by mass. As a method for adding the modified monomer, the modified monomer can be pressured into the reactor through TFE.

[0848] Before the start of the polymerization reaction, or before the polymerization reaction proceeds and the concentration of PTFE in the polymerization dispersion reaches 10.0% by mass, preferably before reaching 5.0% by mass, the amount of the added modified monomer is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, further preferably 0.001% by mass or more, and particularly preferably 0.003% by mass or more with respect to the obtained PTFE. In addition, before the start of the polymerization reaction, or before the polymerization reaction proceeds and the concentration of PTFE in the aqueous dispersion reaches 10.0% by mass, preferably before reaching 5.0% by mass, the amount of the added modified monomer is, in order of preference, 1.0% by mass or less, 0.90% by mass or less, 0.50% by mass or less, 0.40% by mass or less, 0.30% by mass or less, 0.20% by mass or less, 0.15% by mass or less, 0.10% by mass or less, 0.05% by mass or less with respect to the obtained PTFE.

[0849] As the modified monomer, the substances described above that are used as the modified monomer of PTFE contained in the composition constituting the present invention can also be appropriately used in the manufacturing method of the present invention.

[0850] In the manufacturing method of the present invention, the polymerization of TFE can also be stopped by adding a polymerization inhibitor (radical scavenger) to obtain a polymerization dispersion.

[0851] As a polymerization inhibitor, a compound that adds to a free radical in a polymerization system or does not have the ability to re-initiate after chain transfer is used. Specifically, a compound having the following functions is used: easily undergoes a chain transfer reaction with a primary radical or a growing radical, and then generates a stable radical that does not react with the monomer, or easily undergoes an addition reaction with a primary radical or a growing radical to generate a stable radical. The activity of a substance generally referred to as a chain transfer agent is characterized by a chain transfer constant and a re-initiation efficiency. Among chain transfer agents, a substance with a re-initiation efficiency of substantially 0% is called a polymerization inhibitor. As the polymerization inhibitor, at least one selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and copper chloride (CuCl2) is preferably used. As the aromatic hydroxy compound, unsubstituted phenol, polyphenol, salicylic acid, m-salicylic acid or p-salicylic acid, gallic acid, naphthol, etc. can be cited. As the above unsubstituted phenol, o-nitrophenol, m-nitrophenol or p-nitrophenol, o-aminophenol, m-aminophenol or p-aminophenol, p-nitrosophenol, etc. can be cited. As the polyphenol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, naphthoresorcinol, etc. can be cited. As the aromatic amines, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, benzidine, etc. can be cited. As the above quinone compound, hydroquinone, o-benzoquinone, m-benzoquinone or p-benzoquinone, 1,4-naphthoquinone, alizarin, etc. can be cited. As the thiocyanate, ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN), etc. can be cited. Among the above polymerization inhibitors, a quinone compound is preferably used, and hydroquinone is more preferably used.

[0852] From the aspect of reducing the standard specific gravity, the polymerization inhibitor is preferably added before 90% by mass of all the tetrafluoroethylene consumed in the polymerization reaction is polymerized. More preferably, it is added before 85% by mass, and further preferably 80% by mass of all the tetrafluoroethylene is polymerized. In addition, it is preferably added after 5% by mass of all the tetrafluoroethylene consumed in the polymerization reaction is polymerized, and more preferably after 10% by mass is polymerized. The addition amount of the polymerization inhibitor is preferably an amount equivalent to 0.1 mass ppm to 20 mass ppm of the mass of the aqueous medium used, and more preferably an amount equivalent to 3 mass ppm to 10 mass ppm.

[0853] In the manufacturing method of the present invention, it is also preferable to add a decomposing agent. By adding the decomposing agent, the free radical concentration during polymerization can be adjusted. Examples of the decomposing agent include sulfites, bisulfites, bromates, diimines, oxalic acid, copper salts, iron salts, etc. Examples of the sulfite include sodium sulfite and ammonium sulfite. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate. The addition amount of the decomposing agent is added in the range of 25% by mass to 300% by mass relative to the amount of the oxidizing agent combined as the polymerization initiator (the redox initiator described later). As the addition amount of the decomposing agent, it is preferably 25% by mass to 150% by mass, and more preferably 50% by mass to 100% by mass. In addition, it is preferable to add the decomposing agent after 5% by mass of all the tetrafluoroethylene consumed in the polymerization reaction has polymerized, and more preferably after 10% by mass has polymerized. The addition amount of the polymerization inhibitor is preferably an amount equivalent to 0.1 mass ppm to 20 mass ppm of the mass of the aqueous medium used, and more preferably an amount equivalent to 3 mass ppm to 10 mass ppm.

[0854] The polymerization of TFE can be efficiently carried out by using at least one polymer (I). In addition, in the polymerization of TFE, two or more polymers (I) can be used simultaneously for manufacturing. As long as it is a volatile substance or a substance that can remain in the final product, a surfactant can also be used simultaneously for manufacturing.

[0855] The polymerization of TFE can be further carried out in the presence of a nucleating agent.

[0856] As the nucleating agent, it is preferably at least one selected from the group consisting of, for example, fluorinated polyethers, nonionic surfactants, and chain transfer agents.

[0857] In addition, as the nucleating agent used in the manufacturing method of the present invention, since more particles can be generated during polymerization, primary particles with a smaller average primary particle size and aspect ratio can be obtained. A chain transfer agent is more preferably used, and further preferably one or both of a chain transfer agent, a nonionic surfactant, and a fluorinated polyether. When using one or both of a chain transfer agent, a nonionic surfactant, and a fluorinated polyether as the nucleating agent, the nucleating agent includes a combination of a chain transfer agent and a nonionic surfactant, a combination of a chain transfer agent and a fluorinated polyether, and a combination of a chain transfer agent, a nonionic surfactant, and a fluorinated polyether. As the nucleating agent, among them, a combination of a chain transfer agent and a nonionic surfactant is preferably used.

[0858] As the above-mentioned fluorinated polyether, perfluoropolyether is preferably used.

[0859] The above-mentioned fluorinated polyether preferably has repeating units represented by formulas (1a) to (1d).

[0860] (-CFCF3-CF2-O-)n (1a)

[0861] (-CF2-CF2-CF2-O-) n (1b)

[0862] (-CF2-CF2-O-)n-(-CF2-O-) m (1c)

[0863] (-CF2-CFCF3-O-)n-(-CF2-O-) m (1d)

[0864] (In formulas (1a) to (1d), m and n are integers of 1 or more.)

[0865] As the fluorinated polyether, a fluorinated polyether acid or its salt is preferred. As the fluorinated polyether acid, a carboxylic acid, a sulfonic acid, a sulfonamide, or a phosphonic acid is preferred, and a carboxylic acid is more preferred. Among the fluorinated polyether acid or its salt, a salt of the fluorinated polyether acid is preferred, an ammonium salt of the fluorinated polyether acid is more preferred, and an ammonium salt of the fluorinated polyether carboxylic acid is further preferred.

[0866] The fluorinated polyether acid or its salt may have any chain structure in which oxygen atoms in the main chain of the molecule are separated by a saturated fluorocarbon group having 1 to 3 carbon atoms. Two or more types of fluorocarbon groups may be present in the molecule.

[0867] As the above-mentioned fluorinated polyether acid or its salt, the following formula is preferred: CF3-CF2-CF2-O(-CFCF3-CF2-O-) n CFCF3-COOH, CF3-CF2-CF2-O(-CF2-CF2-CF2-O-) n -CF2-CF2COOH or HOOC-CF2-O(-CF2-CF2-O-) n -(-CF2-O-) m CF2COOH (where m and n are the same as above) or their salts.

[0868] These structures were studied by Kasai in J. Appl. Polymer Sci. 57, 797 (1995). As disclosed herein, such a fluorinated polyether may have a carboxylic acid group or its salt at one or both ends. Similarly, such a fluorinated polyether may have a sulfonic acid or phosphonic acid group or its salt at one or both ends. In addition, a fluorinated polyether having acid functional groups at both ends may have different groups at each end. Regarding monofunctional fluorinated polyethers, the other end of the molecule is usually perfluorinated and may also contain hydrogen or chlorine atoms.

[0869] The fluoropolyether having an acid group at one or both ends has at least 2 ether oxygens, preferably at least 4 ether oxygens, and more preferably at least 6 ether oxygens. Preferably, at least one of the fluorinated carbon groups separated by the ether oxygens, more preferably at least two of such fluorinated carbon groups, have 2 or 3 carbon atoms. Even more preferably, at least 50% of the fluorinated carbon groups separated by the ether oxygens have 2 or 3 carbon atoms. In addition, it is preferred that the fluoropolyether has a total of at least 15 carbon atoms, for example, the preferred minimum value of n or n+m in the above repeating unit structure is at least 5. Two or more fluoropolyethers having an acid group at one or both ends can be used in the method of the present invention. Typically, in the manufacture of a single type of specific fluoropolyether compound, unless special attention is paid, the fluoropolyether can contain two or more compounds in various proportions within the molecular weight range relative to the average molecular weight.

[0870] The number average molecular weight of the fluoropolyether is preferably 800 g / mol or more. Since the dispersion of the fluoropolyether acid or its salt in an aqueous medium may be difficult, the number average molecular weight is preferably less than 6000 g / mol. The number average molecular weight of the fluoropolyether acid or its salt is more preferably 800 g / mol to 3500 g / mol, and further preferably 1000 g / mol to 2500 g / mol.

[0871] The amount of the fluoropolyether is preferably 5 to 3000 mass ppm, more preferably 5 to 2000 mass ppm, with respect to the aqueous medium. The further preferred lower limit is 10 mass ppm, and the further preferred upper limit is 100 mass ppm.

[0872] As the nonionic surfactant of the nucleating agent, the above-mentioned nonionic surfactants can be mentioned, and preferably the nonionic surfactants containing no fluorine can be mentioned. For example, ether-type nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, etc.; polyoxyethylene derivatives such as ethylene oxide / propylene oxide block copolymers; ester-type nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters; amine-based nonionic surfactants such as polyoxyethylene alkylamines and alkyl alkanolamides; etc.

[0873] The nonionic surfactant as the nucleating agent is preferably at least one selected from the group consisting of a nonionic surfactant represented by the general formula (i) and a nonionic surfactant represented by the general formula (ii).

[0874] Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, and various halogenated hydrocarbons such as isopentane, methane, ethane, propane, isobutane, methanol, ethanol, isopropanol, acetone, various thiols, carbon tetrachloride, and cyclohexane.

[0875] As the chain transfer agent, a bromine compound or an iodine compound can be used. As a polymerization method using a bromine compound or an iodine compound, for example, a method of polymerizing a fluorine-containing monomer in an aqueous medium in the substantial absence of oxygen in the presence of a bromine compound or an iodine compound (iodine transfer polymerization method) can be mentioned. As a representative example of the bromine compound or iodine compound used, for example, a compound represented by the general formula: R a I x Br y (wherein x and y are each an integer of 0 to 2 and satisfy 1 ≤ x + y ≤ 2, and R a is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, and this R a may or may not contain an oxygen atom) can be mentioned. By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer, and it functions as a crosslinking point.

[0876] Examples of the bromine compound or iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodon-propane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, BrCF2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluoro-1-butene, 2-bromo-4-iodoperfluoro-1-butene, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted benzene, and (2-iodoethyl) and (2-bromoethyl) substituted products, etc. These compounds can be used alone or in combination with each other.

[0877] As a chain transfer agent, among these, from the viewpoints of polymerization reactivity, crosslinking reactivity, ease of acquisition, etc., at least one selected from the group consisting of alkanes and alcohols is preferred. The number of carbon atoms of the alkane is preferably 1 to 6, more preferably 1 to 5, still more preferably 2 to 4, and particularly preferably 3 to 4. In addition, the number of carbon atoms of the alcohol is preferably 1 to 5, more preferably 1 to 4, and further preferably 3 to 4. As the chain transfer agent, at least one selected from the group consisting of methane, ethane, propane, isobutane, methanol, ethanol, and isopropanol is particularly preferred. In addition, as the chain transfer agent, at least one selected from the group consisting of alcohols having 1 to 4 carbon atoms and alkanes having 2 to 4 carbon atoms is preferred, and at least one selected from the group consisting of isopropanol, sec-butanol, and tert-butanol is more preferred. In particular, by using a chain transfer agent containing a tertiary carbon, more particles are generated during polymerization.

[0878] The amount of the above chain transfer agent is preferably 0.001 mass ppm to 10,000 mass ppm with respect to the aqueous medium. The amount of the above chain transfer agent is more preferably 0.01 mass ppm or more, still more preferably 0.05 mass ppm or more, and particularly preferably 0.1 mass ppm or more with respect to the aqueous medium. In addition, it is more preferably 1,000 mass ppm or less, still more preferably 500 mass ppm or less, and particularly preferably 100 mass ppm or less with respect to the aqueous medium.

[0879] The above chain transfer agent can be added to the reaction vessel at once before the start of polymerization, can be added at once after the start of polymerization, can be added in several portions during polymerization, or can also be added continuously during polymerization.

[0880] Next, a particularly suitable embodiment when using at least one selected from the group consisting of fluorinated polyethers, nonionic surfactants, and chain transfer agents as a nucleating agent will be described.

[0881] In the above polymerization, it is preferred to add the nucleating agent to the aqueous medium before the start of the polymerization reaction or before the concentration of PTFE in the aqueous dispersion reaches 5.0% by mass during the polymerization reaction. By adding the nucleating agent in the initial stage of polymerization, more particles can be generated during polymerization, and thus primary particles with a smaller average primary particle size and aspect ratio can be obtained. That is, the nucleating agent can be added before the start of polymerization, can be added simultaneously with the start of polymerization, or can also be added after the start of polymerization and during the period of forming the nuclei of PTFE particles.

[0882] The timing of adding the nucleating agent is before the start of polymerization or before the concentration of PTFE in the aqueous dispersion reaches 5.0% by mass during the polymerization reaction. It is preferably before the start of polymerization or before the PTFE concentration reaches 3.0% by mass, more preferably before the start of polymerization or before the PTFE concentration reaches 1.0% by mass, further preferably before the start of polymerization or before the PTFE concentration reaches 0.5% by mass, and particularly preferably before the start of polymerization or simultaneously with the start of polymerization.

[0883] Regarding the amount of the added nucleating agent, since more particles can be generated during polymerization, primary particles with smaller average primary particle size and aspect ratio can be obtained. Relative to the obtained PTFE, it is preferably 0.001 mass ppm to 5000 mass ppm. As the lower limit of the amount of the nucleating agent, in order of preference, it is 0.01 mass ppm, 0.05 mass ppm, 0.1 mass ppm. As the upper limit of the amount of the nucleating agent, in order of preference, it is 2000 mass ppm, 1000 mass ppm, 500 mass ppm, 100 mass ppm, 50 mass ppm, 10 mass ppm.

[0884] As described above, as the nucleating agent, at least one selected from the group consisting of fluorinated polyethers, nonionic surfactants, and chain transfer agents is preferably used.

[0885] The amount of the fluorinated polyether is preferably 5 ppm to 5000 ppm relative to the aqueous medium. As the lower limit of the amount of the fluorinated polyether, in order of preference, it is 10 mass ppm, 20 mass ppm, 30 mass ppm, 50 mass ppm. As the upper limit of the fluorinated polyether, in order of preference, it is 3000 mass ppm, 2000 mass ppm, 1000 mass ppm, 500 mass ppm, 100 mass ppm.

[0886] The amount of the nonionic surfactant is preferably 0.1% by mass to 0.0000001% by mass relative to the aqueous medium. As the lower limit of the amount of the nonionic surfactant, in order of preference, it is 0.000001% by mass, 0.000005% by mass, 0.00001% by mass. As the upper limit of the amount of the above nonionic surfactant, in order of preference, it is 0.01% by mass, 0.005% by mass, 0.001% by mass, 0.0005% by mass, 0.0001% by mass.

[0887] The amount of the chain transfer agent is preferably 0.001 mass ppm to 10,000 mass ppm relative to the aqueous medium. As the lower limit of the amount of the chain transfer agent, in order of preference, it is 0.01 mass ppm, 0.05 mass ppm, 0.1 mass ppm, 0.5 mass ppm. As the upper limit of the amount of the chain transfer agent, in order of preference, it is 1,000 mass ppm, 500 mass ppm, 100 mass ppm, 10 mass ppm.

[0888] When using a chain transfer agent and a nonionic surfactant as nucleating agents, as the mass ratio of the chain transfer agent to the nonionic surfactant (chain transfer agent / nonionic surfactant), since more particles can be generated during polymerization, and thus primary particles with a smaller average primary particle size and aspect ratio can be obtained, it is preferably 1000 / 1 to 1 / 5, more preferably 200 / 1 to 1 / 2, 100 / 1 to 1 / 1, and further preferably 50 / 1 to 2 / 1.

[0889] The polymerization of TFE can further be carried out in the presence of a nonionic surfactant. As the nonionic surfactant, the substances as described above which are contained in the composition of the present invention and can also be appropriately used in the production method of the present invention can be used.

[0890] The amount of the above nonionic surfactant is preferably 0.1 mass% to 0.0000001 mass% relative to the aqueous medium, and more preferably 0.01 mass% to 0.000001 mass%.

[0891] In the production method of the present invention, when obtaining the polymerization dispersion liquid, it is preferable to add the aqueous medium and the stabilization aid to the reaction vessel, remove the oxygen in the reaction vessel, add tetrafluoroethylene to the reaction vessel, add the polymerization initiator to the reaction vessel, thereby initiating the polymerization reaction of tetrafluoroethylene, and remove the stabilization aid from the polymerization dispersion liquid obtained after the polymerization reaction ends.

[0892] As the stabilization aid, paraffin, fluorinated oil, fluorinated solvent, silicone oil, etc. are preferred. The stabilization aid can be used alone or in combination of two or more. As the stabilization aid, paraffin is more preferred. As paraffin, it can be a liquid, a semi-solid, or a solid at room temperature, but a saturated hydrocarbon having 12 or more carbon atoms is preferred. The melting point of paraffin is usually preferably 40°C to 65°C, and more preferably 50°C to 65°C.

[0893] The amount of the stabilization aid is preferably 0.1 mass% to 12 mass% based on the mass of the aqueous medium used, and more preferably 0.1 mass% to 8 mass%. The stabilization aid is preferably sufficiently hydrophobic and can be completely separated from the polymerization dispersion liquid obtained after the polymerization reaction ends without becoming a contaminating component.

[0894] In addition, in the manufacturing method of the present invention, when obtaining the polymer dispersion liquid, additives for stabilizing each compound can be used. Examples of the above-mentioned additives include buffering agents, pH regulators, dispersion stabilizers, and the like.

[0895] As the polymerization initiator, as long as free radicals can be generated within the above polymerization temperature range, there is no particular limitation, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, polymerization can be initiated in a redox form by combining with a reducing agent or the like. The concentration of the above polymerization initiator is appropriately determined according to the type of monomer, the molecular weight of the target PTFE, and the reaction rate.

[0896] As the above polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0897] As the oil-soluble radical polymerization initiator, known oil-soluble peroxides can be used. Representative substances include the following peroxides: dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; peresters such as tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate; dialkyl peroxides such as di-tert-butyl peroxide; and bis(ω-hydro-dodecafluorocaproyl) peroxide, bis(ω-hydro-tetra-decafluoroheptanoyl) peroxide, bis(ω-hydro-hexa-decafluorononanoyl) peroxide, bis(perfluorobutyryl) peroxide, bis(perfluoropentanoyl) peroxide, bis(perfluorohexanoyl) peroxide, bis(perfluoroheptanoyl) peroxide, bis(perfluorooctanoyl) peroxide, bis(perfluorononanoyl) peroxide, bis(ω-chloro-hexafluorobutyryl) peroxide, bis(ω-chloro-decafluorohexanoyl) peroxide, bis(ω-chloro-tetra-decafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydro-hexa-decafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydro-dodecafluoroheptanoyl-perfluorobutyryl-peroxide, bis(dichloropentafluorobutyryl) peroxide, bis(trichlorooctafluorohexanoyl) peroxide, bis(tetrachloroundecafluorooctanoyl) peroxide, bis(pentachlorotetradecafluorodecanoyl) peroxide, bis(undecachlorotritriacontadifluorodocosanoyl) peroxide, and other bis[perfluoro(or fluorochloro)acyl] peroxides; and so on.

[0898] As the water-soluble radical polymerization initiator, known water-soluble peroxides can be used. Examples include ammonium salts, potassium salts, sodium salts of sulfuric acid, boric acid, perchloric acid, phosphoric acid, carbonic acid, etc., organic peroxides such as disuccinic peroxide and dipimelic peroxide, tert-butyl peroxymaleate, and tert-butyl hydroperoxide. A reducing agent such as sulfite can also be included simultaneously, and its dosage can be 0.1 to 20 times that of the peroxide.

[0899] For example, in the case of carrying out polymerization at a low temperature below 30°C, etc., as the polymerization initiator, a redox initiator composed of a combination of an oxidizing agent and a reducing agent is preferably used. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, ammonium cerium nitrate, bromates, etc. Examples of the reducing agent include sulfites, bisulfites, bromates, diimines, oxalic acid, etc. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the sulfite include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the combination of the redox initiator. Examples of the copper salt include copper(II) sulfate, and examples of the iron salt include iron(II) sulfate.

[0900] Examples of the above-mentioned redox initiator include, for example, potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / iron(II) sulfate, ammonium persulfate / sulfite / iron(II) sulfate, ammonium persulfate / sulfite, ammonium persulfate / iron(II) sulfate, manganese triacetate / oxalic acid, ammonium cerium nitrate / oxalic acid, bromate / sulfite, bromate / bisulfite, etc., and potassium permanganate / oxalic acid and ammonium persulfate / sulfite / iron(II) sulfate are preferred. In the case of using a redox initiator, either the oxidizing agent or the reducing agent can be previously charged into the polymerization kettle, and then the other is continuously or intermittently added to initiate polymerization. For example, in the case of using potassium permanganate / oxalic acid, it is preferable to charge oxalic acid into the polymerization kettle and continuously add potassium permanganate thereto.

[0901] The addition amount of the polymerization initiator is not particularly limited, and it may be added at one time, sequentially, or continuously at the beginning of polymerization in an amount such that the polymerization rate does not decrease significantly (for example, the concentration relative to water is several ppm) or more. The upper limit is in the range where the heat of polymerization reaction can be removed from the equipment surface and the reaction temperature can be increased at the same time, and the more preferable upper limit is in the range where the heat of polymerization reaction can be removed from the equipment surface.

[0902] The above-mentioned aqueous medium is a reaction medium for carrying out polymerization and is a liquid containing water. The above-mentioned aqueous medium is not particularly limited as long as it contains water, and it may contain water and, for example, a non-fluorinated organic solvent such as an alcohol, an ether, or a ketone and / or a fluorinated organic solvent having a boiling point of 40°C or lower.

[0903] In the production method of the present invention, it is preferable to polymerize TFE under conditions where substantially no fluorosurfactant (excluding compounds having a functional group capable of reacting in free radical polymerization and a hydrophilic group) is present. Conventionally, fluorosurfactants have been used in the polymerization of TFE, but in the production method of the present invention, by using the polymer (I), PTFE can be obtained even without using a fluorosurfactant. In the present invention, "under conditions where substantially no fluorosurfactant is present" means that the fluorosurfactant is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and still more preferably 1 mass ppb or less relative to the aqueous medium.

[0904] Examples of the fluorosurfactant include the fluorosurfactants as described above that can be contained in the composition of the present invention.

[0905] In addition, as the polymer (I), a polymer (I) in which the content of the dimer and trimer of the monomer (hereinafter sometimes referred to as monomer (I)) represented by the general formula (I) is 1.0 mass% or less relative to the polymer (I) can also be used.

[0906] That is, the production method of the present invention also preferably includes the following steps:

[0907] A step of polymerizing the monomer (I) represented by the general formula (I) in an aqueous medium to obtain a crude composition containing the polymer of the monomer (I);

[0908] A step of removing the dimer and trimer of the monomer (I) contained in the above crude composition from the above crude composition to obtain a polymer (I) in which the content of the dimer and trimer of the monomer (I) is 1.0 mass% or less relative to the polymer (I);

[0909] A step of polymerizing TFE in an aqueous medium in the presence of the polymer (I) to obtain a polymerization dispersion containing PTFE, the polymer (I), and the aqueous medium; and

[0910] A step of mixing the above polymerization dispersion with a nonionic surfactant to obtain a composition containing PTFE, the polymer (I), the nonionic surfactant, and the aqueous medium.

[0911] The polymer (I) used in the above manufacturing method substantially does not contain the dimer and trimer of monomer (I). The dimer and trimer of monomer (I) are usually generated when monomer (I) is polymerized to obtain polymer (I). As the content of the dimer and trimer in polymer (I), it is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, further preferably 0.001% by mass or less, and particularly preferably 0.0001% by mass or less relative to polymer (I).

[0912] Regarding the content of the dimer and trimer in polymer (I), by performing gel permeation chromatography (GPC) analysis on polymer (I) and calculating the ratio (area percentage) of the total peak area of the dimer and trimer to the total area of each peak in the chromatogram obtained by GPC analysis, it can be specified.

[0913] In addition, when the content of the dimer and trimer in polymer (I) is less than 0.5% by mass relative to polymer (I), it can be specified by measurement using liquid chromatography - tandem mass spectrometry (LC / MS / MS).

[0914] Specifically, an aqueous solution with a content of monomer (I) at 5 levels or more is prepared, LC / MS / MS analysis is performed on each content, a graph is plotted of the relationship between the content and the area (peak integral value) of the region relative to that content, and a calibration curve of monomer (I) is made. Furthermore, a calibration curve of the dimer and trimer of monomer (I) is made from the calibration curve of monomer (I).

[0915] Methanol is added to polymer (I) to prepare a mixture, the extract (supernatant) is recovered from the mixture by centrifugation, and LC / MS / MS analysis is performed on the obtained extract.

[0916] Then, using the calibration curve, the area (peak integral value) of the region of the chromatogram of the dimer and trimer of monomer (I) can be converted into the content of the dimer and trimer.

[0917] By using polymer (I) substantially free of dimer and trimer during the polymerization of TFE in an aqueous medium, a polymerization dispersion substantially free of the dimer and trimer of monomer (I) can be produced.

[0918] Polymer (I) is a polymer containing polymerization unit (I) based on monomer (I). The polymer (I) used in the present invention is a polymer obtained by substantially removing dimer (a polymer containing 2 polymerization units (I)) and trimer (a polymer containing 3 polymerization units (I)) from a polymer (I) containing 2 or more polymerization units (I).

[0919] The molecular weight of monomer (I) is preferably 400 or less. That is, polymer (I) preferably substantially does not contain dimers and trimers having a molecular weight of 1200 or less.

[0920] The dimers and trimers of polymer (I) may be polymers formed from one type of monomer (I) as the monomer (I) represented by the general formula (I), or may be copolymers formed from two or more types of monomers (I) having different structures.

[0921] The polymerization of monomer (I) can be carried out by a known method. By using this method to produce a crude composition, a crude composition in which polymer (I) is dispersed or dissolved in an aqueous medium can be obtained.

[0922] The polymerization of monomer (I) is preferably carried out in an aqueous medium under conditions where a fluorosurfactant (except for the monomer (I) represented by the general formula (I)) is substantially absent.

[0923] In the present invention, "under conditions where a fluorosurfactant is substantially absent" means that the amount of the fluorosurfactant relative to the aqueous medium is 10 mass ppm or less. As the amount of the fluorosurfactant relative to the aqueous medium, it is preferably 1 mass ppm or less, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and still more preferably 1 mass ppb or less.

[0924] Regarding the fluorosurfactant, as described above.

[0925] In the crude composition thus obtained, as polymers of monomer (I), dimers and trimers in total usually exceed 1.0 mass% relative to the mass of the polymers of monomer (I). The content of dimers and trimers in the polymers of monomer (I) can be, for example, 2.0 mass% or more, 3.0 mass% or more, 30.0 mass% or less, or 20.0 mass% or less relative to the polymers of monomer (I). Regarding the content of dimers and trimers in the crude composition, gel permeation chromatography (GPC) analysis of the crude composition is performed, and the ratio (area percentage) of the total peak area of dimers and trimers to the total area of each peak in the chromatogram obtained by GPC analysis is calculated, whereby it can be specified.

[0926] Next, the dimers and trimers of monomer (I) contained in the crude composition obtained by the polymerization of monomer (I) are removed from the crude composition. The means for removing dimers and trimers is not particularly limited, and at least one means selected from the group consisting of ultrafiltration, microfiltration, and dialysis membrane treatment is preferred, at least one means selected from the group consisting of microfiltration and dialysis membrane treatment is more preferred, and ultrafiltration is further preferred.

[0927] The polymerization of monomer (I) generates the dimer and trimer of monomer (I), and as a result, the polymer (I) contains the dimer and trimer of monomer (I), which has not been known in the past. The mechanism for generating the dimer and trimer of monomer (I) is not necessarily clear, but it is speculated that: especially in the monomers present in the polymerization system, through the polymerization reaction in the polymerization system where monomer (I) accounts for the majority, the dimerization and trimerization of monomer (I) occur at a non-negligible frequency. In the present invention, the presence of the dimer and trimer of monomer (I) in polymer (I) is first clearly identified, and it is first discovered that the dimer and trimer of monomer (I) in polymer (I) (crude composition) can be efficiently removed from polymer (I) by at least one means selected from the group consisting of ultrafiltration, microfiltration, and dialysis membrane treatment.

[0928] When removing the dimer and trimer, usually, the unreacted monomer (I) is also removed from the crude composition at the same time. Even when the unreacted monomer (I) is introduced into PTFE through polymerization, it does not necessarily have an adverse effect on the function of PTFE, so the unreacted monomer (I) does not necessarily have to be removed. However, by removing the unreacted monomer (I) simultaneously with the dimer and trimer in advance, the amount of monomer for polymerization can be calculated without considering the presence of the unreacted monomer (I), and it has the advantage of being able to easily manufacture PTFE with a desired monomer composition. It should be noted that even when monomer (I) remains in polymer (I) or when monomer (I) is newly added as a comonomer, in the monomers present in the polymerization system, through the polymerization reaction in the polymerization system where fluorine-containing monomers (excluding monomer (I)) account for the majority, the dimerization and trimerization of monomer (I) are basically not carried out, and the dimer and trimer of monomer (I) hardly remain in the obtained PTFE.

[0929] The crude composition obtained by the polymerization of monomer (I) can be the composition after polymerization obtained during polymerization, or a substance obtained by diluting or concentrating the composition after polymerization obtained during polymerization, or a substance that has been subjected to dispersion stabilization treatment, etc. In order to smoothly carry out ultrafiltration, microfiltration, or dialysis membrane treatment, it is also preferable to adjust the viscosity of the crude composition through these treatments.

[0930] The content of the polymer of monomer (I) in the crude composition is not particularly limited and may be, for example, 0.1% by mass to 20% by mass. From the aspect of the removal efficiency of the dimer and trimer, the content of the polymer of monomer (I) in the crude composition is preferably 18.0% by mass or less, more preferably 15.0% by mass or less, still more preferably 12.0% by mass or less, particularly preferably 10.0% by mass or less, and preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.2% by mass or more, particularly preferably 1.5% by mass or more. The content of the polymer of monomer (I) in the crude composition can be adjusted, for example, by a method of adding water to the crude composition obtained by the polymerization of monomer (I), a method of concentrating the crude composition obtained by the polymerization of monomer (I), etc.

[0931] The pH of the crude composition is preferably 0 to 11, more preferably 0.5 to 8.0, still more preferably 1.0 to 7.0. The pH of the crude composition can be adjusted by adding a pH regulator to the crude composition obtained by the polymerization of monomer (I). As the pH regulator, an acid or a base can be used, and examples thereof include phosphates, sodium hydroxide, potassium hydroxide, ammonia water, etc.

[0932] In order to smoothly perform ultrafiltration, microfiltration or dialysis membrane treatment, the viscosity of the crude composition is preferably 25 mPa·s or less. The viscosity of the crude composition can be adjusted, for example, by a method of adjusting the number average molecular weight of the polymer of monomer (I), a method of adjusting the concentration of the polymer of monomer (I) in the crude composition, a method of adjusting the temperature of the crude composition, etc.

[0933] The above ultrafiltration or microfiltration can be in a cross-flow mode or a dead-end mode, and there is no limitation. From the aspect of reducing membrane fouling, the cross-flow mode is preferred.

[0934] The above ultrafiltration can be carried out using an ultrafiltration membrane. Ultrafiltration can be carried out, for example, using an ultrafiltration device having an ultrafiltration membrane, and centrifugal ultrafiltration, batch ultrafiltration, circulation ultrafiltration, etc. can be adopted.

[0935] The molecular weight cut-off of the above ultrafiltration membrane is usually about 0.1×10 4 Da to 30×10 4 Da. Since the above ultrafiltration membrane can inhibit membrane fouling and effectively reduce dimers and trimers, the molecular weight cut-off is preferably 1.5×10 4 Da or more. The above molecular weight cut-off is more preferably 2.0×10 4 Da or more, particularly preferably 3.0×10 4 Da or more, most preferably 5.0×10 4 Da or more. The above molecular weight cut-off can also be 8.0×104 Da or more. In addition, from the aspect of the removal efficiency of dimers and trimers, the above-mentioned molecular weight cut-off is preferably 20×10 4 Da or less, more preferably 10×10 4 Da or less.

[0936] Regarding the molecular weight cut-off of the above ultrafiltration membrane, for example, polystyrene with a known weight-average molecular weight can be passed through the membrane, and the molecular weight that can block 90% is taken as the molecular weight cut-off. The quantification of polystyrene can be carried out using gel permeation chromatography.

[0937] As the shape of the above ultrafiltration membrane, known shapes in the art can be cited, without limitation, such as hollow fiber type, flat membrane type, spiral type, tube type, etc. From the aspect of suppressing blockage, the hollow fiber type is preferred.

[0938] The inner diameter of the hollow fiber type ultrafiltration membrane is not limited, and can be, for example, 0.1 mm to 2 mm. Preferably it is 0.8 mm to 1.4 mm.

[0939] The length of the hollow fiber type ultrafiltration membrane is not limited, and can be, for example, 0.05 m to 3 m. Preferably it is 0.05 m to 2 m.

[0940] As the material of the ultrafiltration membrane, there is no particular limitation, and organic materials such as cellulose, cellulose ester, polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, chlorinated polyethylene, polypropylene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, metals such as stainless steel, or inorganic materials such as ceramics can be cited.

[0941] The material of the ultrafiltration membrane is preferably an organic material, more preferably chlorinated polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, polysulfone or polyethersulfone, and further preferably polyacrylonitrile or polyvinylidene fluoride.

[0942] As the above ultrafiltration membrane, specifically, G-5 type, G-10 type, G-20 type, G-50 type, PW type, HWS UF type of DESAL company can be cited; HFM-180, HFM-183, HFM-251, HFM-300, HFM-116, HFM-183, HFM-300, HFK-131, HFK-328, MPT-U20, MPS-U20P, MPS-U20S of KOCH company; SPE1, SPE3, SPE5, SPE10, SPE30, SPV5, SPV50, SOW30 of Synder company; Microza (registered trademark) UF series manufactured by Asahi Kasei Corporation; NTR7410 manufactured by Nitto Denko Corporation, etc.

[0943] From the aspect of the removal efficiency of dimers and trimers, the above ultrafiltration is preferably carried out under a pressure of 0.01 MPa or more. More preferably, it is 0.03 MPa or more, and further preferably 0.05 MPa or more. In addition, from the aspect of pressure resistance, the above pressure is preferably 0.5 MPa or less, more preferably 0.25 MPa or less, and further preferably 0.2 MPa or less.

[0944] From the aspect of the removal efficiency of dimers and trimers, the above ultrafiltration is preferably carried out at a flow rate of 10 mL / min or more, more preferably at a flow rate of 50 mL / min or more. In addition, it is preferably carried out at a flow rate of 5000 mL / min or less, more preferably at a flow rate of 1000 mL / min or less.

[0945] The above microfiltration can be carried out using a microfiltration membrane. The microfiltration membrane usually has an average pore diameter of 0.05 μm to 1.0 μm.

[0946] Since it can effectively remove dimers and trimers, the average pore diameter of the above microfiltration membrane is preferably 0.1 μm or more. More preferably, it is 0.075 μm or more, and further preferably 0.1 μm or more. In addition, the average pore diameter is preferably 1.00 μm or less. The average pore diameter is more preferably 0.50 μm or less, and further preferably 0.25 μm or less.

[0947] The average pore diameter of the above microfiltration membrane can be measured according to ASTM F316 03 (bubble point method).

[0948] As the shape of the above microfiltration membrane, known shapes can be cited, and there is no limitation. For example, hollow fiber type, flat membrane type, spiral type, tube type, etc. can be cited. From the aspect of suppressing clogging, the hollow fiber type is preferred.

[0949] The inner diameter of the hollow fiber type ultrafiltration membrane is not limited. For example, it can be 0.1 mm to 2 mm. It is preferably 0.8 mm to 1.4 mm.

[0950] The length of the hollow fiber type ultrafiltration membrane is not limited. For example, it can be 0.05 m to 3 m. It is preferably 0.05 m to 2 m.

[0951] As the material of the above microfiltration membrane, for example, cellulose-based, aromatic polyamide, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, polytetrafluoroethylene, ceramics, metals, etc. can be cited. Among them, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate or polytetrafluoroethylene is preferred, and polyacrylonitrile or polyvinylidene fluoride is particularly preferred.

[0952] As the microfiltration membrane, specifically, Cefilt manufactured by NGK Insulators, Ltd.; Microza U series and Microza P series manufactured by Asahi Kasei Corporation; Poreflon SPMW, Poreflon OPMW, and Poreflon PM manufactured by Sumitomo Electric Industries, Ltd.; Trefil manufactured by Toray Industries, Inc.; NADIR MP005 and NADIR MV020 manufactured by MICRODYN-NADIR GmbH; X-flow manufactured by Norit B.V. etc. may be mentioned.

[0953] From the aspect of the removal efficiency of dimers and trimers, the above-mentioned microfiltration is preferably carried out at a pressure of 0.01 MPa or more. More preferably, it is 0.03 MPa or more, and further preferably 0.05 MPa or more. In addition, from the aspect of pressure resistance, the above-mentioned pressure is preferably 0.5 MPa or less, more preferably 0.25 MPa or less, and further preferably 0.2 MPa or less.

[0954] From the aspect of the removal efficiency of dimers and trimers, the above-mentioned microfiltration is preferably carried out at a flow rate of 10 mL / min or more, more preferably at a flow rate of 50 mL / min or more. In addition, it is preferably carried out at a flow rate of 5000 mL / min or less, more preferably at a flow rate of 1000 mL / min or less.

[0955] The above-mentioned dialysis membrane treatment is carried out using a dialysis membrane. The dialysis membrane usually has a cut-off molecular weight of 0.05×10 4 Da to 100×10 4 Da.

[0956] Since the above-mentioned dialysis membrane can inhibit the clogging of the membrane and effectively remove dimers and trimers, the cut-off molecular weight is preferably 0.3×10 4 Da or more. The above-mentioned cut-off molecular weight is more preferably 0.5×10 4 Da or more, further preferably 1.0×10 4 Da or more, still more preferably 1.5×10 4 Da or more, particularly preferably 2.0×10 4 Da or more, especially preferably 3.0×10 4 Da or more, most preferably 5.0×10 4 Da or more. The above-mentioned cut-off molecular weight may also be 8.0×10 4 Da or more.

[0957] In addition, from the aspect of the removal efficiency of dimers and trimers, the above-mentioned cut-off molecular weight is preferably 20×10 4 Da or less, more preferably 10×10 4 Da or less.

[0958] The cut-off molecular weight of the above dialysis membrane can be measured, for example, by the same method as that for ultrafiltration membranes.

[0959] As the material of the above dialysis membrane, there is no particular limitation, and examples thereof include cellulose, polyacrylonitrile, polymethyl methacrylate, ethylene-vinyl alcohol copolymer, polysulfone, polyamide, polyester-based polymer alloy, etc.

[0960] As the dialysis membrane, specifically, examples thereof include Spectra / Por (registered trademark) Float-A-Lyzer, Tube-A-Lyzer, Dialysis tubing, 6Dialysistubing, 7Dialysis tubing, etc. manufactured by Spectrum Laboratories.

[0961] The above ultrafiltration, microfiltration or dialysis membrane treatment is preferably carried out at a temperature of 10°C or higher. More preferably, it is 15°C or higher, further preferably 20°C or higher, and particularly preferably 30°C or higher. By setting the temperature within the above range, dimers and trimers can be more effectively reduced. The above temperature is preferably 90°C or lower, more preferably 80°C or lower, further preferably 70°C or lower, and particularly preferably 60°C or lower.

[0962] Regarding the ultrafiltration, microfiltration or dialysis membrane treatment, water can be added to the crude composition or the pH of the crude composition can be adjusted while carrying out the treatment. Water can be added to the crude composition intermittently or continuously.

[0963] The end point of the ultrafiltration, microfiltration or dialysis membrane treatment can be appropriately determined without limitation. In addition, in the above ultrafiltration, microfiltration or dialysis membrane treatment, in order to improve the durability of the filter membrane, backwashing can be carried out once or so with water based on a filtration time of 1 hour to 24 hours.

[0964] By removing the dimers and trimers of monomer (I) from the crude composition of the polymer containing monomer (I), generally, an aqueous solution containing polymer (I) substantially free of dimers and trimers is obtained. The polymer (I) used in the above manufacturing method can be the polymer (I) contained in the obtained aqueous solution or the polymer (I) separated from the aqueous solution. The method for separating polymer (I) from the aqueous solution is not particularly limited. For example, polymer (I) can be separated by methods such as precipitation, washing, and drying of polymer (I) in the aqueous solution.

[0965] As polymer (I), an aqueous solution containing polymer (I) can be used. The preferred content of the dimers and trimers of monomer (I) relative to polymer (I) in the aqueous solution is the same as the content of the dimers and trimers in polymer (1).

[0966] In the production method of the present invention, after obtaining a polymerization dispersion by polymerizing TFE, the obtained polymerization dispersion is mixed with a nonionic surfactant. As the nonionic surfactant, the substances described above, which are the nonionic surfactants contained in the composition of the present invention, can also be suitably used in the production method of the present invention.

[0967] The mixing ratio of the polymerization dispersion and the nonionic surfactant is not particularly limited, and it is preferable to mix the polymerization dispersion and the nonionic surfactant in a ratio such that the preferred content of the nonionic surfactant in the composition of the present invention is obtained.

[0968] The production method of the present invention preferably further includes the following step: concentrating the composition to obtain a concentrated composition. By concentrating the composition, the content of PTFE in the composition can be appropriately adjusted, and a large amount of the composition containing PTFE can also be produced.

[0969] Examples of the concentration method include phase separation concentration, ion exchanger method, membrane concentration, etc. Phase separation concentration, ion exchanger method, and membrane concentration can be carried out under conventionally known treatment conditions, and there is no particular limitation. The methods described in International Publication No. 2004 / 050719 pamphlet, Japanese Patent Application Laid-Open No. 2002-532583, and Japanese Patent Application Laid-Open No. 55-120630 can be used. Among them, phase separation concentration is preferred as the concentration method. Phase separation concentration is usually carried out by adding a nonionic surfactant.

[0970] Phase separation concentration can be carried out, for example, in the following manner: heating a composition containing PTFE, polymer (I), a nonionic surfactant, and an aqueous medium, thereby phase-separating into a phase (supernatant phase) not containing a fluoropolymer and a phase (concentrated phase) containing a fluoropolymer, removing the phase not containing a fluoropolymer, and recovering the phase (concentrated phase) containing a fluoropolymer, whereby it can be carried out.

[0971] The recovered phase (concentrated phase) containing a fluoropolymer contains a fluoropolymer and an aqueous medium, and contains polymer (1) in a reduced amount compared to before concentration.

[0972] Phase separation concentration can be carried out by standing at a temperature not lower than 10 °C lower than the cloud point of the nonionic surfactant used. In addition, the above phase separation concentration can be carried out by standing at a temperature not higher than 10 °C higher than the cloud point.

[0973] In the production method of the present invention, it is also preferable to repeat phase separation concentration. The number of repetitions is not particularly limited, and it is preferably 2 or more times, more preferably 3 or more times. The upper limit of the number of times is not limited. For example, it may be 10 or less times. By repeating phase separation concentration, the content of the polymer (1) can be further reduced.

[0974] In the case of performing phase separation concentration 2 or more times, the first phase separation concentration is preferably carried out by heating at a temperature of 5°C or more lower than the cloud point of the nonionic surfactant and then allowing to stand, separating into a supernatant phase and a concentrated phase. The heating temperature is more preferably 3°C or more lower than the cloud point, further preferably at or above the cloud point, and particularly preferably heating above the cloud point. In addition, the second or subsequent phase separation concentration is preferably carried out by heating at a temperature of 5°C or more lower than the cloud point of the nonionic surfactant and then allowing to stand, separating into a supernatant phase and a concentrated phase. The heating temperature is more preferably 3°C or more lower than the cloud point, and particularly preferably heating to the cloud point.

[0975] By the production method of the present invention described above, the first composition of the present invention can be appropriately produced.

[0976] The second composition of the present invention can be appropriately produced by the following production method, which includes: a step of polymerizing TFE in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I) to obtain a polymerization dispersion containing PTFE, the polymer (I), and the aqueous medium; and a step of concentrating the polymerization dispersion by phase separation concentration to obtain the above composition.

[0977] Regarding the step of obtaining the polymerization dispersion, it can have the above configuration except that a nonionic surfactant can be arbitrarily added.

[0978] In the production method of the second composition of the present invention, after obtaining a polymerization dispersion by polymerizing TFE, the polymerization dispersion is concentrated by phase separation concentration.

[0979] Phase separation concentration can be carried out by the following method: heating a polymerization dispersion containing PTFE, the polymer (I), and the aqueous medium, thereby phase-separating into a phase (supernatant phase) not containing a fluoropolymer and a phase (concentrated phase) containing a fluoropolymer, removing the phase not containing a fluoropolymer, and recovering the phase (concentrated phase) containing a fluoropolymer, whereby it can be carried out.

[0980] Before phase separation concentration, the polymer dispersion can be mixed with a nonionic surfactant to prepare a composition containing PTFE, polymer (I), nonionic surfactant, and an aqueous medium, and the resulting composition can be subjected to phase separation concentration. In this case, the phase separation concentration can be carried out as follows: the above composition is heated to a temperature above the temperature 10°C lower than the cloud point of the nonionic surfactant, phase-separated into a supernatant phase and a concentrated phase, and the concentrated phase is recovered to obtain a concentrated composition, whereby it can be carried out.

[0981] The recovered phase containing the fluoropolymer (concentrated phase) contains the fluoropolymer and an aqueous medium, and contains polymer (1) in a reduced amount compared to before concentration.

[0982] The phase separation concentration can be carried out by allowing it to stand at a temperature above the temperature 10°C lower than the cloud point of the nonionic surfactant. In addition, the phase separation concentration can be carried out by allowing it to stand at a temperature below the temperature 10°C higher than the cloud point.

[0983] It is also preferable to repeat the phase separation concentration. The number of repetitions is not particularly limited, preferably 2 or more times, more preferably 3 or more times. The upper limit of the number of times is not limited, for example, it can also be 10 or less times. By repeating the phase separation concentration, the content of polymer (1) can be further reduced.

[0984] In the case of carrying out phase separation concentration 2 or more times, the first phase separation concentration is preferably carried out by heating at a temperature above the temperature 5°C lower than the cloud point of the nonionic surfactant and then allowing it to stand, separating into a supernatant phase and a concentrated phase. The temperature of the above heating is more preferably above the temperature 3°C lower than the cloud point, further preferably above the cloud point, and particularly preferably heating above the cloud point. In addition, the second or subsequent phase separation concentration is preferably carried out by heating at a temperature above the temperature 5°C lower than the cloud point of the nonionic surfactant and then allowing it to stand, separating into a supernatant phase and a concentrated phase. The temperature of the above heating is more preferably above the temperature 3°C lower than the cloud point, and particularly preferably heating to the cloud point.

[0985] The production method of the present invention may further include a step of mixing the concentrated composition with an anionic hydrocarbon surfactant. By adding an anionic surfactant to the concentrated composition, even when the composition contains a large amount of PTFE, the viscosity of the composition can be appropriately adjusted, or the miscibility of pigments, fillers, etc. can be improved.

[0986] The third composition of the present invention can be suitably produced, for example, by the following production method, which includes: a step of polymerizing TFE in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), thereby obtaining a polymerization dispersion containing PTFE, the polymer (I), and the aqueous medium; a step of mixing the polymerization dispersion and a nonionic surfactant, thereby obtaining a composition containing PTFE, the polymer (I), the nonionic surfactant, and the aqueous medium; a step of concentrating the composition by phase separation concentration to obtain a concentrated composition; and a step of adding an anionic hydrocarbon surfactant to the concentrated composition.

[0987] As the anionic hydrocarbon surfactant, the substances described above as the anionic hydrocarbon surfactant that can be contained in the composition of the present invention can also be suitably used in the production method of the present invention.

[0988] The mixing ratio of the concentrated composition and the anionic hydrocarbon surfactant is not particularly limited, and it is preferable to mix the concentrated composition and the anionic hydrocarbon surfactant in a ratio to obtain the preferable content of the anionic hydrocarbon surfactant in the composition of the present invention.

[0989] The production method of the present invention may further include a step of mixing the concentrated composition and a preservative. By adding a preservative to the concentrated composition, a composition that inhibits spoilage and bacterial growth can be produced even in the case of long-term storage.

[0990] The production method of the present invention may include the following step: bringing a composition containing PTFE, the polymer (I), the nonionic surfactant, and the aqueous medium into contact with an anion exchange resin or a mixed bed containing an anion exchange resin and a cation exchange resin. This ion exchange treatment is preferably carried out before concentrating the composition.

[0991] Examples of the anion exchange resin include strongly basic anion exchange resins having a -N + X - (CH3)3 group (X represents Cl or OH) as a functional group, strongly basic anion exchange resins having a -N + X - (CH3)3(C2H4OH) group (X is the same as above) as a functional group, and other known anion exchange resins. Specifically, the anion exchange resins described in WO99 / 062858, WO03 / 020836, WO2004 / 078836, WO2013 / 027850, WO2014 / 084399, etc. can be mentioned.

[0992] The cation exchange resin is not particularly limited, and examples thereof include well-known cation exchange resins such as a strongly acidic cation exchange resin having -SO3 - group as a functional group, and a weakly acidic cation exchange resin having -COO - group as a functional group. Among them, from the viewpoint of removal efficiency, a strongly acidic cation exchange resin is preferably used, and an H + type strongly acidic cation exchange resin is more preferably used.

[0993] The "mixed bed containing a cation exchange resin and an anion exchange resin" is not particularly limited, and includes cases where both are filled in the same column, cases where both are filled in different columns, cases where both are dispersed in an aqueous dispersion, etc.

[0994] The above describes the embodiments, but it is understood that various changes can be made to the embodiments and details without departing from the gist and scope of the claims.

[0995] Examples

[0996] Next, examples are given to illustrate the embodiments of the present invention, but the present invention is not limited to the described examples.

[0997] The respective numerical values in the examples were measured by the following methods.

[0998] <Average primary particle size>

[0999] The PTFE aqueous dispersion was diluted with water to a solid content concentration of 0.15% by mass, and the transmittance of the transmitted light at 550 nm of the obtained diluted emulsion with respect to the unit length and the number-based length average primary particle size determined by measuring the orientation diameter from a transmission electron microscope photograph were measured to prepare a calibration curve. Using this calibration curve, the average primary particle size was determined from the actually measured transmittance of the transmitted light at 550 nm of each sample.

[1000] In addition, the average primary particle size can be measured by dynamic light scattering method. In the dynamic light scattering method, an aqueous dispersion of a fluoropolymer with the solid content concentration of the fluoropolymer adjusted to about 1.0% by mass was prepared, and measurement was performed at 25 °C with 70 integrations using ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.). The refractive index of the solvent (water) was 1.3328, and the viscosity of the solvent (water) was 0.8878 mPa·s.

[1001] <Standard specific gravity (SSG)>

[1002] Using a sample molded according to ASTM D 4895-89, measurement was performed by the water displacement method according to ASTM D 792.

[1003] <Content of modified monomer unit>

[1004] The content of PMVE units is determined from the spectrum obtained by solid 19 F-MAS NMR measurement using the following formula.

[1005] X = (4B / 3) / (A+(B / 3))×100

[1006] X: Content of PMVE units (mol%)

[1007] A: Integration value of the signal at -120 ppm

[1008] B: Integration value of the CF signal at -52 ppm

[1009] The chemical shift value is the value when the peak top of the signal from the PTFE main chain is set to -120 ppm.

[1010] <Solid component concentration>

[1011] 1 g of the PTFE aqueous dispersion is dried in a forced-air dryer under the conditions of 150 °C for 60 minutes, and the value representing the ratio of the mass of the heating residue to the mass of the aqueous dispersion (1 g) is used, expressed as a percentage.

[1012] <Contents of polymer A and polymer D>

[1013] The contents of polymer A and polymer D contained in the PTFE powder are determined from the spectrum obtained by solid 19 F-MAS NMR measurement.

[1014] Y = (4B / (5A+3B))×100

[1015] Y: Content of polymer A or polymer D (mol%)

[1016] A: Integration value of the signal at -120 ppm

[1017] B: Sum of the integration values of the CF2 and CF3 signals at -83 ppm

[1018] The chemical shift value is the value when the peak top of the signal from the PTFE main chain is set to -120 ppm.

[1019] <Aspect ratio>

[1020] The PTFE aqueous dispersion with the solid component concentration diluted to about 1 mass% is observed using a scanning electron microscope (SEM), image processing is performed on more than 400 randomly extracted particles, and it is determined from the average value of the ratio of the major axis to the minor axis.

[1021] <Content of non-ionic surfactant>

[1022] Weigh approximately 1 g (X g) of the sample into an aluminum cup with a diameter of 5 cm, heat it at 110 °C for 30 minutes to obtain the heated residue (Y g). Further, heat the obtained heated residue (Y g) at 300 °C for 30 minutes to obtain the heated residue (Z g). Calculate the content of the non-ionic surfactant (N mass %) according to the formula: N = [(Y - Z) / X] × 100 (mass %) based on the heated residue (Y g) and the heated residue (Z g).

[1023] <Mechanical stability test>

[1024] Add 100 g of the PTFE aqueous dispersion into a plastic cup with a diameter of 67 mm and an inner volume of 300 ml, soak it in a water bath at 60 °C, and place a stirring blade with a diameter of 50 mm ( Figure 1 ) so that the height from the bottom of the plastic cup to the center of the stirring blade ( Figure 1 (in the axial direction of (b), at a position 6 mm below the lower end of the stirring blade)) is 20 mm, rotate it at 3000 rpm, and measure the time until the PTFE aqueous dispersion coagulates or solidifies and scatters as the stability retention time.

[1025] <Viscosity>

[1026] Measure the viscosity at 25 °C using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., rotor No. 2) under the conditions of a rotational speed of 60 rpm and a measurement time of 120 seconds. It should be noted that when the viscosity is above 80 mPa·s, during the viscosity measurement, the viscosity will increase with the measurement time. Therefore, measure the viscosity 5 minutes and 10 minutes after the start of the measurement and take the average value.

[1027] <Sedimentation stability test>

[1028] Add 25 ml of the PTFE aqueous dispersion into a graduated stoppered test tube with a tube body diameter of 18 mm, a total height of 215 mm, and a capacity of 25 ml, and place it at 20 °C - 30 °C for 18 hours. Then, insert a pipette into the test tube in such a way that the tip of the pipette is at the liquid level height of the PTFE aqueous dispersion, and collect 3 ml of the PTFE aqueous dispersion as the upper phase sample. Next, insert a pipette into the test tube in such a way that the tip of the pipette is at the liquid level height of the PTFE aqueous dispersion, and collect 19 ml of the PTFE aqueous dispersion. Take the remaining 3 ml of the PTFE aqueous dispersion in the test tube as the lower phase sample. Measure the solid component concentrations of the upper phase sample and the lower phase sample by the above method, and calculate the difference in the solid component concentrations between the upper phase sample and the lower phase sample. The smaller the difference, the better the sedimentation stability.

[1029] <Method for Determining Contents of Dimer and Trimer of Monomer D in Polymer D and Method for Determining Contents of Dimer and Trimer of Monomer E in Polymer E>

[1030] (1) Extraction from Aqueous Solution

[1031] Determine the solid content of the aqueous solution of the polymer, and weigh an amount of the aqueous solution equivalent to 0.2 g of the solid content of the polymer. Then, combine it with the water contained in the aqueous solution, and add water and methanol in such a way that the volume ratio of water to methanol is 50 / 50 (volume %), to obtain a mixed solution containing the polymer, water, and methanol. Then, use the obtained mixed solution to perform centrifugation at 4000 rpm for 1 hour, and recover the supernatant containing the polymer as the extract.

[1032] Analyze the extract using a liquid chromatography mass spectrometer (Waters, LC-MS ACQUITY UPLC / TQD) to obtain a chromatogram of the extract.

[1033] Regarding the contents of the dimer and trimer of the monomer contained in the extract, convert the integral values of the peaks of the dimer and trimer of the monomer appearing in the chromatogram of the extract into the contents of the dimer and trimer of the monomer using a calibration curve, and thus obtain them.

[1034] (2) Calibration Curve of Monomer

[1035] Prepare 5 levels of methanol standard solutions of the monomer with known contents from 1 ng / mL to 100 ng / mL, and perform measurements using a liquid chromatography mass spectrometer (Waters, LC-MS ACQUITY UPLC / TQD). Plot the relationship between the content of each monomer and the integral value of the peak corresponding to that content to make a calibration curve (first approximation) for each monomer. Then, use the calibration curve (first approximation) of each monomer to make calibration curves for the dimer and trimer of each monomer.

[1036] Composition of Measuring Equipment and LC-MS Measuring Conditions

[1037]

Table 1

[1038] Table 1

[1039]

[1040] The quantification limit in the composition of this measuring equipment is 1 ng / mL.

[1041] The surfactants (a) and (b) used in the examples are as follows.

[1042] Surfactant (a): T-Det A138 manufactured by Harcros Organics

[1043] Surfactant (b): Noigen TDS-80 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[1044] <Polymer A>

[1045] A homopolymer (number average molecular weight 9.0×10 4 , weight average molecular weight 19.0×10 4 )(hereinafter referred to as Polymer A). The ion exchange capacity of Polymer A is 3.67 meq / g.

[1046] <Method for measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of polymers (such as Polymer A, D, E, etc.)>

[1047] Regarding the number average molecular weight and weight average molecular weight of the polymer, gel permeation chromatography (GPC) was used. Using GPC HLC-8020 manufactured by Tosoh Corporation, columns manufactured by Shodex Corporation (one GPC KF-801, one GPC KF-802, and two GPC KF-806M connected in series) were used, and tetrahydrofuran (THF) as a solvent was passed through at a flow rate of 1 ml / min for measurement, and the molecular weight was calculated using monodisperse polystyrene as a standard.

[1048] Synthesis Example 1

[1049] 3560 g of deionized water, 180 g of paraffin wax, and 5.37 g of polymer A were added to a 6 L SUS reactor equipped with a stirrer. Ammonia water was added to adjust the pH to 9.1. Then, while heating the contents of the reactor to 70 °C, suction was performed and purged with TFE to remove the oxygen in the reactor, and the contents were stirred. After adding 0.54 g of PMVE to the reactor, TFE was added until the pressure reached 0.73 MPaG. 17.9 mg of ammonium persulfate (APS) initiator dissolved in 20 g of deionized water was injected into the reactor to make the pressure of the reactor 0.83 MPaG. After injecting the initiator, a pressure drop occurred, and the start of polymerization was observed. TFE was added to the reactor to keep the pressure constant at 0.78 MPaG. When the amount of TFE consumed in the reaction reached about 180 g, the supply of TFE and stirring were stopped. Then, the gas in the reactor was slowly released until the pressure of the reactor reached 0.02 MPaG. After that, TFE was supplied until the pressure of the reactor reached 0.78 MPaG, stirring was started again, and the reaction was continued. When the amount of TFE consumed in the reaction reached about 1250 g, the supply of TFE was stopped and stirring was stopped to end the reaction. After that, the gas was exhausted until the pressure inside the reactor reached atmospheric pressure, and the contents were taken out of the reactor and cooled. The supernatant paraffin wax was removed to obtain PTFE aqueous dispersion A.

[1050] The solid content concentration of PTFE aqueous dispersion A was 24.5% by mass, the average primary particle size was 375 nm, and the aspect ratio was 1.67. The concentration of polymer A contained in PTFE aqueous dispersion A relative to PTFE was 0.43% by mass.

[1051] Production Example 1

[1052] PTFE aqueous dispersion A was diluted with deionized water to a solid content concentration of about 10% by mass, solidified under high-speed stirring conditions, and the obtained wet powder was dried at 210 °C for 18 hours. The SSG of the obtained PTFE powder was 2.182, the PMVE content was 0.011% by mass, and the polymer A content was 0.43% by mass.

[1053] Example 1

[1054] Phase separation concentration

[1055] Surfactant (a) was added to PTFE aqueous dispersion A in an amount of 30 parts by mass relative to 100 parts by mass of PTFE, and held at 47 °C for 3 hours to separate into a supernatant phase and a concentrated phase. The concentrated phase was recovered to obtain PTFE aqueous dispersion 1.

[1056] The solid content concentration of the PTFE aqueous dispersion 1 is 56.7% by mass, and the content of the surfactant (a) is 3.0% by mass relative to PTFE.

[1057] The PTFE aqueous dispersion 1 was diluted with deionized water to a solid content concentration of about 10% by mass, solidified under high-speed stirring conditions, and the obtained wet powder was dried at 210 °C for 18 hours.

[1058] The content of polymer A is 0.15% by mass relative to PTFE. That is, the concentration of polymer A relative to the PTFE aqueous dispersion 1 is 0.15% by mass. In addition, the concentration of polymer A relative to PTFE is 0.26% by mass.

[1059] The viscosity of the PTFE aqueous dispersion 1 is 138.2 mPa·s, the stability retention time is 8.3 minutes, and the difference in solid content concentration between the upper-phase sample and the lower-phase sample is 1.0% by mass.

[1060] Example 2

[1061] Surfactant (a) was added to the PTFE aqueous dispersion A in an amount of 3.0 parts by mass relative to 100 parts by mass of PTFE. The viscosity of the obtained PTFE aqueous dispersion is 6.2 mPa·s, the stability retention time is 1.5 minutes, and the difference in solid content concentration between the upper-phase sample and the lower-phase sample is 31.7% by mass.

[1062] Preparation Example 1

[1063] 220 g of monomer D represented by CH2=CF(CF2OCFCF3COOH), 513 g of water were added to the reactor, and further ammonium persulfate (APS) at 0.5 mol% relative to monomer D was added. It was heated and stirred at 60 °C for 24 hours in a nitrogen atmosphere to obtain an aqueous solution D-1 of polymer D containing polymer D which is a homopolymer of CH2=CF(CF2OCFCF3COOH). GPC analysis was performed on the obtained aqueous solution D-1 of polymer D. As a result, the Mw of polymer D was 180,000, the Mn was 86,000, and the content of the dimer and trimer was 2.0% by mass relative to polymer D. The ion exchange capacity of polymer D was 3.67 meq / g.

[1064] Water was added to the obtained aqueous solution D-1 of polymer D to adjust the concentration of polymer D to 5.0% by mass. Then, ultrafiltration was carried out by contacting an ultrafiltration membrane (molecular weight cut-off: 50,000 Da, made of polyethylene) at 30 °C under a water pressure of 0.1 MPa. Ultrafiltration was continued while appropriately injecting water until the filtrate eluted 7 times the amount of water relative to the aqueous solution, and an aqueous solution D-2 of polymer D was obtained. GPC analysis was performed on the obtained aqueous solution D-2 of polymer D. As a result, the Mw of polymer D was 180,000 and the Mn was 140,000, and the contents of the dimer and trimer were less than 1 mass ppm relative to polymer D. The concentration of the obtained aqueous solution D-2 of polymer D was 5.0% by mass.

[1065] Synthesis Example 2

[1066] The amount of deionized water was changed to 3452.6 g, 107.4 g of the aqueous solution D-2 of polymer D was added instead of 5.37 g of polymer A, ammonia water was added to adjust the pH to 8.7, 0.01 g of isopropanol was added, 2.4 g of HFP was added instead of 0.54 g of PMVE, and 25.1 mg of ammonium persulfate (APS) and 537 mg of dibenzoyl peroxide (DSP) were added instead of 17.9 mg of ammonium persulfate (APS) initiator. Polymerization was carried out in the same manner as in Synthesis Example 1, and the supply was stopped when the amount of TFE was about 1450 g. A PTFE aqueous dispersion D was obtained in the same manner as in Synthesis Example 1.

[1067] The solid content concentration of the PTFE aqueous dispersion D was 29.1% by mass, the average primary particle size was 250 nm, and the aspect ratio was 1.61. The concentration of polymer D contained in the PTFE aqueous dispersion D relative to PTFE was 0.37% by mass.

[1068] Production Example 2

[1069] Using the PTFE aqueous dispersion D, PTFE powder was obtained in the same manner as in Production Example 1. The SSG of the PTFE powder was 2.201, the HFP content was 0.063% by mass, and the content of polymer D was 0.37% by mass.

[1070] Example 3

[1071] A surfactant (b) was added to the PTFE aqueous dispersion D in an amount of 15 parts by mass relative to 100 parts by mass of PTFE, and the mixture was maintained at 62 °C for 12 hours and separated into a supernatant phase and a concentrated phase. The concentrated phase was recovered to obtain a PTFE aqueous dispersion 3.

[1072] The solid content concentration of the PTFE aqueous dispersion 3 was 62.0% by mass, and the content of the surfactant (b) relative to PTFE was 3.5% by mass.

[1073] The surfactant (b) was added to the PTFE aqueous dispersion 3 in an amount of 5.5% by mass relative to PTFE. Ammonium lauryl sulfate at 1000 ppm by mass relative to PTFE was further added. Deionized water and ammonia water were further added to obtain the PTFE aqueous dispersion 3-1.

[1074] The solid content concentration of the PTFE aqueous dispersion 3-1 was 61.1% by mass, and the content of the surfactant (b) was 5.4% by mass relative to PTFE.

[1075] The concentration of Polymer D in the PTFE aqueous dispersion 3-1 was 0.09% by mass. Additionally, the concentration of Polymer D relative to PTFE was 0.15% by mass.

[1076] A sample of about 5 g of the PTFE aqueous dispersion 3-1 was weighed, 10 ml of methanol was added, the sample was poured into a cylindrical filter paper, and Soxhlet extraction was carried out such that the total amount of methanol as the extraction solvent was 100 ml. The obtained extract was appropriately concentrated by nitrogen purging to obtain an extract. The obtained extract was subjected to LC / MS / MS measurement. It should be noted that the detection limit in the measurement was 0.5 ppb by mass. None of the following compounds and monomer D shown by the following formula were detected.

[1077] F(CF2)7COOM,

[1078] F(CF2)5COOM,

[1079] H(CF2)6COOM,

[1080] CF3O(CF2)3OCHFCF2COOM,

[1081] C3F7OCF(CF3)CF2OCF(CF3)COOM,

[1082] CF3CF2CF2OCF(CF3)COOM,

[1083] CF3CF2OCF2CF2OCF2COOM,

[1084] C2F5OCF(CF3)CF2OCF(CF3)COOM,

[1085] CF3OCF(CF3)CF2OCF(CF3)COOM,

[1086] CF2ClCF2CF2OCF(CF3)CF2OCF2COOM,

[1087] CF2ClCF2CF2OCF2CF(CF3)OCF2COOM,

[1088] CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM,

[1089] CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM,

[1090]

Chemical 28

[1091]

[1092] (In each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents.)

[1093] The viscosity of the PTFE aqueous dispersion 3-1 is 53.3 mPa·s, the stability retention time is 11.7 minutes, and the difference in the solid component concentration between the upper-phase sample and the lower-phase sample is 0.50 mass%.

[1094] Example 4

[1095] 239 parts by mass of deionized water and 17 parts by mass of surfactant (b) relative to 100 parts by mass of PTFE were added to the PTFE aqueous dispersion 3, and it was kept at 58 °C for 12 hours and separated into a supernatant phase and a concentrated phase. The concentrated phase was recovered to obtain the PTFE aqueous dispersion 4.

[1096] Surfactant (b) was added to the obtained PTFE aqueous dispersion 4 in an amount of 5.5 mass% relative to PTFE, ammonium lauryl sulfate at 2000 ppm relative to PTFE was further added, and deionized water and ammonia water were further added to obtain the PTFE aqueous dispersion 4-1.

[1097] The solid component concentration of the obtained PTFE aqueous dispersion 4-1 is 60.3 mass%, and the content of surfactant (b) is 5.5 mass% relative to PTFE.

[1098] The concentration of polymer D relative to the PTFE aqueous dispersion 4-1 is 0.06 mass%. In addition, the concentration of polymer D relative to PTFE is 0.10 mass%.

[1099] The viscosity of the PTFE aqueous dispersion 4-1 is 36.1 mPa·s, the stability retention time is 10.8 minutes, and the difference in the solid component concentration between the upper-phase sample and the lower-phase sample is 0.67 mass%.

[1100] Preparation Example 2

[1101] 10 g of monomer E represented by CF2=CFOCF2CF2COOH, 30 g of water, and ammonium persulfate (APS) (6.0 mol% relative to monomer E) were added to a reactor, and the mixture was heated and stirred at 80 °C for 23 hours under a nitrogen atmosphere to obtain an aqueous solution E-1 of polymer E containing a homopolymer of CF2=CFOCF2CF2COOH as polymer E. GPC analysis was performed on the obtained aqueous solution E-1 of polymer E. As a result, the Mw of polymer E was 7,000 and the Mn was 5,000. The ion exchange capacity of polymer E was 4.13 meq / g.

[1102] Water was added to the obtained aqueous solution E-1 of polymer E, and filtration was carried out by contacting a dialysis membrane (cut-off molecular weight: 35,000 Da, made of polyethylene) at 30 °C to obtain an aqueous solution E-2 of polymer E. GPC analysis was performed on the obtained aqueous solution E-2 of polymer E. As a result, the Mw of polymer E was 7,000 and the Mn was 6,000, and the contents of the dimer and trimer were less than 1 ppm relative to polymer E. The concentration of the obtained aqueous solution E-2 of polymer E was 3.6% by mass.

[1103] Synthesis Example 3

[1104] 515 g of deionized water, 30 g of paraffin, 15.28 g of the aqueous solution E-2 of polymer E, and ammonia water were added to a glass reactor with a stirrer having an internal volume of 1 L, and the pH was adjusted to 9.2. Then, while heating the contents of the reactor to 70 °C, suction was performed, and at the same time, the inside of the reactor was purged with TFE monomer to remove oxygen. After that, the contents were stirred at 540 rpm. After adding 0.13 g of PMVE to the reactor, TFE monomer was added until the pressure reached 0.73 MPaG.

[1105] 2.75 mg of ammonium persulfate (APS) initiator dissolved in 20 g of deionized water was injected into the reactor to make the pressure in the reactor 0.83 MPaG. After injecting the initiator, a pressure drop occurred, and the start of polymerization was observed. TFE monomer was added to the reactor to maintain the pressure, and polymerization was continued until the reaction of about 140 g of TFE monomer was completed. After that, the pressure was exhausted until the pressure inside the reactor reached atmospheric pressure, and the contents were taken out of the reactor and cooled. The supernatant paraffin was removed to obtain a PTFE aqueous dispersion E.

[1106] The solid content concentration of the obtained PTFE aqueous dispersion E was 21.0% by mass, the average primary particle size was 216 nm, and the aspect ratio was 1.22. The concentration of polymer E contained in the PTFE aqueous dispersion E relative to PTFE was 0.35% by mass.

[1107] Production Example 3

[1108] Using the obtained PTFE aqueous dispersion E, PTFE powder was obtained in the same manner as in Production Example 1. The SSG of the obtained PTFE powder was 2.168, the PMVE modification amount was 0.072% by mass, and the content of polymer E was 0.35% by mass.

[1109] Example 5

[1110] A surfactant (b) was added to the PTFE aqueous dispersion E in an amount of 15 parts by mass relative to 100 parts by mass of PTFE, and the mixture was maintained at 62 °C for 12 hours and separated into a supernatant phase and a concentrated phase. The concentrated phase was recovered to obtain a PTFE aqueous dispersion 5. The solid content concentration of the PTFE aqueous dispersion 5 was 63.2% by mass, and the content of the surfactant (b) relative to PTFE was 2.9% by mass.

[1111] The surfactant (b) was additionally added to the obtained PTFE aqueous dispersion 5 in an amount of 5.5% by mass relative to PTFE, ammonium lauryl sulfate at 1000 ppm relative to PTFE was further added, and deionized water and ammonia water were further added to obtain a PTFE aqueous dispersion 5-1.

[1112] The solid content concentration of the obtained PTFE aqueous dispersion 5-1 was 60.6% by mass, and the content of the surfactant (b) relative to PTFE was 5.5% by mass.

[1113] The concentration of polymer E relative to the PTFE aqueous dispersion 5-1 was 0.08% by mass. In addition, the concentration of polymer E relative to PTFE was 0.13% by mass.

[1114] The viscosity of the PTFE aqueous dispersion 5-1 was 51.1 mPa·s, the stability retention time was 13.2 minutes, and the difference in solid content concentration between the upper phase sample and the lower phase sample was 0.32% by mass.

Claims

1. A composition, which is a composition containing polytetrafluoroethylene, a polymer (I) containing a polymerization unit (I) based on a monomer represented by the general formula (I), a nonionic surfactant, and an aqueous medium, wherein, the content of the polytetrafluoroethylene in the composition is 10% by mass or more relative to the composition, the content of the nonionic surfactant in the composition is 1.0% by mass or more relative to the polytetrafluoroethylene, CX 1 X 3 = CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, alkyl or fluoroalkyl; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, alkyl or fluoroalkyl; m is an integer of 1 or more.

2. The composition according to claim 1, wherein the stability retention time of the composition measured by a mechanical stability test is 1.0 minute or more.

3. The composition according to claim 1 or 2, wherein the content of the polytetrafluoroethylene in the composition is 40% by mass or more relative to the composition.

4. The composition according to any one of claims 1 to 3, wherein, The nonionic surfactant is represented by the general formula (i), R 6 -O-A 1 -H(i) In the formula, R 6 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.

5. The composition according to any one of claims 1 to 4, which substantially does not contain a fluorosurfactant.

6. The composition according to any one of claims 1 to 5, wherein, The weight-average molecular weight of the polymer (I) is 2.0×10 4 or more.

7. The composition according to any one of claims 1 to 6, wherein, The weight-average molecular weight of the polymer (I) is 15.0×10 4 or more.

8. The composition according to any one of claims 1 to 7, wherein, The ion exchange capacity of the polymer (I) is 1.75 meg / g or more.

9. The composition according to any one of claims 1 to 8, wherein The ion exchange capacity of the polymer (I) is 2.60 meg / g or more.

10. The composition according to any one of claims 1 to 9, wherein, The polymer (I) is water-soluble.

11. The composition according to any one of claims 1 to 10, wherein, A in general formula (I) 0 is -SO3M, -COOM or -P(O)(OM)2, where in each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, and R 7 is H or an organic group.

12. The composition according to any one of claims 1 to 11, wherein, The polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units.

13. The composition according to claim 12, wherein, The modified monomer is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group and a hydrophilic group capable of reacting in a radical polymerization.

14. A method for producing a composition, which comprises the following steps: a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on a monomer represented by the general formula (I) to obtain a polymerization dispersion containing polytetrafluoroethylene, the polymer (I), and an aqueous medium; and a step of mixing the polymerization dispersion and a nonionic surfactant to obtain a composition containing polytetrafluoroethylene, the polymer (I), the nonionic surfactant, and an aqueous medium, CX 1 X 3 = CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) Wherein, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, alkyl or fluoroalkyl; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, alkyl or fluoroalkyl; m is an integer of 1 or more.

15. The manufacturing method according to claim 14, wherein, The nonionic surfactant is represented by the general formula (i), R 6 -O-A 1 -H(i) In the formula, R 6 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.

16. The manufacturing method according to claim 14 or 15, wherein, tetrafluoroethylene is polymerized under conditions where a fluorosurfactant is substantially absent, provided that the fluorosurfactant does not include a compound having a functional group and a hydrophilic group capable of reacting in a radical polymerization.

17. The manufacturing method according to any one of claims 14 to 16, wherein, When obtaining the polymerization dispersion, an aqueous medium and a stabilization aid are added to a reaction vessel, oxygen in the reaction vessel is removed, tetrafluoroethylene is added to the reaction vessel, and a polymerization initiator is added to the reaction vessel to initiate a polymerization reaction of tetrafluoroethylene, the stabilization aid is removed from the polymerization dispersion obtained after the polymerization reaction ends.

18. The manufacturing method according to any one of claims 14 to 17, wherein, The weight-average molecular weight of the polymer (I) is 2.0×10 4 or more.

19. The manufacturing method according to any one of claims 14 to 18, wherein, The weight-average molecular weight of the polymer (I) is 15.0×10 4 or more.

20. The manufacturing method according to any one of claims 14 to 19, wherein, The ion exchange capacity of the polymer (I) is 1.75 meg / g or more.

21. The manufacturing method according to any one of claims 14 to 20, wherein The ion exchange capacity of the polymer (I) is 2.60 meg / g or more.

22. The manufacturing method according to any one of claims 14 to 21, wherein, The polymer (I) is water-soluble.

23. The manufacturing method according to any one of claims 14 to 22, wherein A in general formula (I) 0 is -SO3M, -COOM or -P(O)(OM)2, in each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R 7 is H or an organic group.

24. The production method according to any one of claims 14 to 23, which further comprises the following step: concentrating the composition to obtain a concentrated composition.

25. The manufacturing method according to claim 24, wherein, When concentrating the composition, the composition is heated to a temperature higher than the cloud point of the nonionic surfactant by 5 °C or more, phase-separated into a supernatant phase and a concentrated phase, and the concentrated phase is recovered, whereby a concentrated composition is obtained.

26. The manufacturing method according to any one of claims 14 to 25, wherein, Polymerize tetrafluoroethylene and a modified monomer capable of copolymerizing with tetrafluoroethylene.

27. The manufacturing method according to any one of claims 14 to 26, wherein, Before initiating the polymerization reaction or before the polymerization reaction proceeds and the concentration of the polytetrafluoroethylene in the polymerization dispersion reaches 5.0% by mass, a modified monomer capable of copolymerizing with tetrafluoroethylene is added to the reaction vessel.

28. The manufacturing method according to claim 26 or 27, wherein, The modified monomer is at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and a modified monomer having a functional group and a hydrophilic group capable of reacting in free radical polymerization.

29. The production method according to any one of claims 14 to 28, further comprising the following step: bringing the composition into contact with an anion exchange resin or a mixed bed containing an anion exchange resin and a cation exchange resin.

30. A composition comprising polytetrafluoroethylene, a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), a nonionic surfactant, and an aqueous medium, wherein The content of the polymer (I) is 2000 mass ppm or less relative to the composition, CX 1 X 3 = CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) In the formula, X 1 and X 3 are each independently F, Cl, H or CF3; X 2 is H, F, an alkyl group or a fluoroalkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 are each independently H, F, an alkyl group or a fluoroalkyl group; m is an integer of 1 or more.

31. The composition according to claim 30, wherein, The content of the polymer (I) is 0.1 mass ppm or more relative to the composition.

32. The composition according to claim 30 or 31, wherein, The content of the polytetrafluoroethylene is 40% by mass or more relative to the composition.

33. The composition according to any one of claims 30 to 32, further containing an anionic hydrocarbon surfactant.

34. The composition according to any one of claims 30 to 33, wherein, The nonionic surfactant is represented by the general formula (i), R 6 -O-A 1 -H(i) In the formula, R 6 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.

35. The composition according to any one of claims 30 to 34, wherein, The content of the nonionic surfactant is 1.0% by mass or more relative to the polytetrafluoroethylene.

36. A production method for producing the composition according to any one of claims 30 to 35, comprising the following steps: A step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), thereby obtaining a polymerization dispersion containing polytetrafluoroethylene, the polymer (I), and an aqueous medium; and A step of concentrating the polymerization dispersion by phase separation concentration to obtain the composition.

37. The manufacturing method according to claim 36, wherein, Repeat the phase separation concentration two or more times.

38. A production method for producing the composition according to any one of claims 30 to 35, comprising the following steps: A step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a polymer (I) containing a polymerization unit (I) based on the monomer represented by the general formula (I), thereby obtaining a polymerization dispersion containing polytetrafluoroethylene, the polymer (I), and an aqueous medium; A step of mixing the polymerization dispersion and a nonionic surfactant to obtain a composition containing polytetrafluoroethylene, the polymer (I), the nonionic surfactant, and an aqueous medium; and When concentrating the composition, the composition is heated to a temperature higher than 5°C lower than the cloud point of the nonionic surfactant, phase-separated into a supernatant phase and a concentrated phase, and the concentrated phase is recovered, whereby a concentrated composition is obtained.

39. The manufacturing method according to claim 38, wherein, The phase separation concentration is repeated two or more times.

40. A composition containing polytetrafluoroethylene, a nonionic surfactant, an anionic hydrocarbon surfactant, and an aqueous medium, and substantially free of fluorosurfactants.

41. The composition according to claim 40, wherein, The fluorosurfactant is a fluorine-containing anionic fluorosurfactant having a molecular weight of 800 or less in the anionic moiety.

42. The composition according to claim 40 or 41, wherein, The content of the fluorosurfactant is 100 mass ppb or less.

43. The composition according to any one of claims 40 to 42, wherein, The fluorosurfactant is F(CF2)7COOM, F(CF2)5COOM, H(CF2)6COOM, CF3O(CF2)3OCHFCF2COOM, C3F7OCF(CF3)CF2OCF(CF3)COOM, CF3CF2CF2OCF(CF3)COOM, CF3CF2OCF2CF2OCF2COOM, C2F5OCF(CF3)CF2OCF(CF3)COOM, CF3OCF(CF3)CF2OCF(CF3)COOM, CF2ClCF2CF2OCF(CF3)CF2OCF2COOM, CF2ClCF2CF2OCF2CF(CF3)OCF2COOM, CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM, CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, and [Chemical 29] The compounds shown, wherein in each formula, M is H, a metal atom, NR 7 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents.

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