Method for manufacturing polytetrafluoroethylene

Abstract

Provided is a method for producing polytetrafluoroethylene, characterized in that the production method includes a polymerization step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant, the amount of the hydrocarbon surfactant at the start of polymerization exceeding 50 ppm relative to the aqueous medium, and the polytetrafluoroethylene contains 99.0% by mass or more of polymerization units based on tetrafluoroethylene and 1.0% by mass or less of polymerization units based on the modified monomer.

Description

[0001] This application is a divisional application. The application number of the original application is 201980062691.9, the filing date is October 3, 2019, and the invention title is "Method for manufacturing polytetrafluoroethylene". Technical Field

[0002] The present invention relates to a method for manufacturing polytetrafluoroethylene. Background Art

[0003] In the case of manufacturing polytetrafluoroethylene by emulsion polymerization, a fluorine-containing anionic surfactant is used. Recently, it has also been proposed to use a hydrocarbon-based surfactant in place of the fluorine-containing anionic surfactant.

[0004] Patent Document 1 describes a method for polymerizing a fluorine-containing monomer in a polymerization reactor to form a dispersion of fluorine-containing polymer particles in an aqueous medium. The method includes an initial period and a stabilization period after the initial period. The initial period includes a step of preparing an initial dispersion of fluorine-containing polymer particles in the aqueous medium in the polymerization reactor. The stabilization period includes a step of polymerizing a fluorine-containing monomer in the polymerization reactor and a step of adding a hydrocarbon-containing surfactant to the polymerization reactor. During the stabilization period, no fluorine-based surfactant is added.

[0005] Patent Document 2 describes a method for polymerizing a fluorine-containing monomer in a polymerization reactor to form a dispersion of fluorine-containing polymer particles in an aqueous medium. The method includes an initial period that includes steps of adding (a) an aqueous medium, (b) a water-soluble hydrocarbon compound, (c) a decomposer, (d) a fluorine-containing monomer, and (e) a polymerization initiator to the polymerization reactor. During the initial period, no fluorine-based surfactant is added, and the decomposer is added before the polymerization initiator.

[0006] Patent Document 3 describes a method for polymerizing a fluorine-containing monomer in a polymerization reactor to form a dispersion of fluorine-containing polymer particles in an aqueous medium. The method includes a step of adding an aqueous medium, a polymerization initiator, a fluorine-containing monomer, and a hydrocarbon-containing surfactant to the polymerization reactor; and a step of deactivating the hydrocarbon-containing surfactant.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: U.S. Patent Publication No. 9,255,164

[0010] Patent Document 2: U.S. Patent Publication No. 8,563,670

[0011] Patent Document 3: U.S. Patent Gazette No. 9,074,025 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] In the present invention, an object is to provide a manufacturing method capable of manufacturing polytetrafluoroethylene by polymerizing a hydrocarbon surfactant, and further, to manufacture polytetrafluoroethylene having a small average primary particle diameter even though it is polymerized using a hydrocarbon surfactant.

[0014] Means for Solving the Problems

[0015] The present invention relates to a method for manufacturing polytetrafluoroethylene, characterized in that the manufacturing method includes a polymerization step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant to obtain polytetrafluoroethylene, the amount of the hydrocarbon surfactant at the start of polymerization exceeds 50 ppm with respect to the aqueous medium, and the above polytetrafluoroethylene contains 99.0% by mass or more of polymerization units based on tetrafluoroethylene and 1.0% by mass or less of polymerization units based on the modified monomer.

[0016] The manufacturing method of the present invention preferably further includes the following step: adding the modified monomer to the aqueous medium before the start of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0% by mass or less. The amount of the modified monomer added before the start of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0% by mass or less is preferably 0.0001% by mass or more with respect to the obtained polytetrafluoroethylene.

[0017] In the polymerization step, the number of polytetrafluoroethylene particles is preferably 0.6×10 13 / mL or more.

[0018] The polymerization step preferably includes a step of continuously adding a hydrocarbon surfactant.

[0019] In the above step of continuously adding a hydrocarbon surfactant, it is preferable to start adding the hydrocarbon surfactant to the aqueous medium when the concentration of polytetrafluoroethylene formed in the aqueous medium is less than 0.6% by mass.

[0020] In the above polymerization step, the polymerization temperature is preferably 10°C to 150°C.

[0021] The above modified monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene.

[0022] The above-mentioned modified monomer preferably includes a modified monomer having a functional group capable of reacting in free radical polymerization and a hydrophilic group. The above-mentioned modified monomer having a functional group capable of reacting in free radical polymerization and a hydrophilic group is preferably the following formula (4):

[0023] CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4)

[0024] (In the formula, X i , X j and X k are each independently F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a linking group; Z 1 and Z 2 are each independently H, F or CF3, and k is 0 or 1) the compound shown.

[0025] The above-mentioned hydrocarbon surfactant is preferably a carboxylic acid type hydrocarbon surfactant.

[0026] The above-mentioned polymerization step is preferably carried out under conditions substantially free of fluorosurfactants.

[0027] The above-mentioned polytetrafluoroethylene preferably has a core-shell structure.

[0028] The average primary particle size of the above-mentioned polytetrafluoroethylene is preferably 500 nm or less.

[0029] The aspect ratio of the primary particles of the above-mentioned polytetrafluoroethylene is preferably 1.45 or less.

[0030] Effects of the Invention

[0031] According to the present invention, a manufacturing method can be provided, which can manufacture polytetrafluoroethylene by using the polymerization of a hydrocarbon surfactant. Furthermore, even though it is the polymerization of a hydrocarbon surfactant, polytetrafluoroethylene with a small average primary particle size can be manufactured. Detailed Embodiments

[0032] In this specification, unless otherwise specified, 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.

[0033] Examples of the "organic group" include:

[0034] An alkyl group that may have one or more substituents,

[0035] An alkenyl group which may have one or more substituents,

[0036] An alkynyl group which may have one or more substituents,

[0037] A cycloalkyl group which may have one or more substituents,

[0038] A cycloalkenyl group which may have one or more substituents,

[0039] A cycloalkadienyl group which may have one or more substituents,

[0040] An aryl group which may have one or more substituents,

[0041] An aralkyl group which may have one or more substituents,

[0042] A non-aromatic heterocyclic group which may have one or more substituents,

[0043] A heteroaryl group which may have one or more substituents,

[0044] Cyano group,

[0045] Formyl group,

[0046] RaO-,

[0047] RaCO-,

[0048] RaSO2-,

[0049] RaCOO-,

[0050] RaNRaCO-,

[0051] RaCONRa-,

[0052] RaOCO-, and,

[0053] RaOSO2-

[0054] (In these formulas, Ra is independently

[0055] An alkyl group which may have one or more substituents,

[0056] An alkenyl group which may have one or more substituents,

[0057] An alkynyl group which may have one or more substituents,

[0058] A cycloalkyl group which may have one or more substituents,

[0059] A cycloalkenyl group which may have one or more substituents,

[0060] A cycloalkadienyl group which may have one or more substituents,

[0061] An aryl group that may have more than one substituent,

[0062] An aralkyl group that may have more than one substituent,

[0063] A non-aromatic heterocyclic group that may have more than one substituent, or

[0064] A heteroaryl group that may have more than one substituent).

[0065] As the above organic group, an alkyl group that may have more than one substituent is preferred.

[0066] In this specification, unless otherwise specified, "substituent" refers to a group that can substitute. Examples of such "substituents" include: aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, acyloxy groups, acylamino groups, aliphatic oxy groups, aromatic oxy groups, heterocyclic oxy groups, aliphatic oxycarbonyl groups, aromatic oxycarbonyl groups, heterocyclic oxycarbonyl groups, carbamoyl groups, aliphatic sulfonyl groups, aromatic sulfonyl groups, heterocyclic sulfonyl groups, aliphatic sulfonyloxy groups, aromatic sulfonyloxy groups, heterocyclic sulfonyloxy groups, sulfamoyl groups, aliphatic sulfonamide groups, aromatic sulfonamide groups, heterocyclic sulfonamide groups, amino groups, aliphatic amino groups, aromatic amino groups, heterocyclic amino groups, aliphatic oxycarbonylamino groups, aromatic oxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxyl groups, cyano groups, sulfo groups, carboxyl groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, di-aliphatic oxyphosphinyl groups or di-aromatic oxyphosphinyl groups.

[0067] The above aliphatic 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. As the above aliphatic group, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, vinyl, cyclohexyl, carbamoylmethyl, etc., can be mentioned.

[0068] 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 6 to 10 carbon atoms in total, such as phenyl, 4-nitrophenyl, 4-acetylaminophenyl, 4-methylsulfonylphenyl, etc., can be mentioned.

[0069] The above heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the above heterocyclic group, 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., can be cited.

[0070] The above acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the above acyl group, an acyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as acetyl group, propionyl group, benzoyl group, 3-pyridinecarbonyl group, etc., can be cited.

[0071] The above acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. As the above acylamino group, 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 an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc., can be cited.

[0072] The above 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. As the above aliphatic oxycarbonyl group, an alkoxycarbonyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, etc., can be cited.

[0073] The above carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. As the above carbamoyl group, 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 an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N-phenylcarbamoyl group, etc., can be cited.

[0074] The above 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. As the above aliphatic sulfonyl group, an alkylsulfonyl group having 1 to 6 carbon atoms in total, preferably 1 to 4 carbon atoms in total, such as a methanesulfonyl group, etc., can be cited.

[0075] The above-mentioned aromatic sulfonyl group may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. As the above-mentioned aromatic sulfonyl group, an arylsulfonyl group having 6 to 10 carbon atoms in total, such as a benzenesulfonyl group, can be mentioned.

[0076] The above-mentioned amino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc.

[0077] 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, an acylamino group having 2 to 12 carbon atoms in total, preferably 2 to 8 carbon atoms in total, and more preferably an alkylcarbonylamino group 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.

[0078] 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.

[0079] 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.

[0080] The above-mentioned aliphatic oxy group may be saturated or unsaturated, and 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, an alkoxy group 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.

[0081] The above-mentioned aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused to 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.

[0082] The above aliphatic thio groups may be saturated or unsaturated. Additionally, examples of alkylthio groups having a total carbon atom number of 1 to 8, more preferably 1 to 6, include methylthio, ethylthio, carbamoylmethylthio, tert-butylthio, and the like.

[0083] The above carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, or the like. Examples of the carbamoylamino group include carbamoylamino, alkylcarbamoylamino having a total carbon atom number of 2 to 9, dialkylcarbamoylamino having a total carbon atom number of 3 to 10, arylcarbamoylamino having a total carbon atom number of 7 to 13, and heterocycliccarbamoylamino having a total carbon atom number of 3 to 12. Preferred are carbamoylamino, alkylcarbamoylamino having a total carbon atom number of 2 to 7, dialkylcarbamoylamino having a total carbon atom number of 3 to 6, arylcarbamoylamino having a total carbon atom number of 7 to 11, and heterocycliccarbamoylamino having a total carbon atom number of 3 to 10. Examples include carbamoylamino, methylcarbamoylamino, N,N-dimethylcarbamoylamino, phenylcarbamoylamino, 4-pyridinecarbamoylamino, and the like.

[0084] The specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0085] The method for producing polytetrafluoroethylene [PTFE] of the present invention includes a polymerization step of polymerizing tetrafluoroethylene [TFE] and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant to obtain PTFE.

[0086] Therefore, according to the production method of the present invention, polytetrafluoroethylene can be produced by polymerization using a hydrocarbon surfactant.

[0087] Furthermore, in the production method of the present invention, at the start of polymerization, a hydrocarbon surfactant in an amount exceeding 50 ppm is present with respect to the aqueous medium. Thereby, polytetrafluoroethylene having a small average primary particle size and a small aspect ratio can be produced. That is, by polymerizing TFE and a modified monomer in an aqueous medium, an aqueous dispersion containing particles of polytetrafluoroethylene is generally obtained. However, according to the production method of the present invention, even though a hydrocarbon surfactant is used to polymerize TFE and a modified monomer, particles having a small average primary particle size and a small aspect ratio can be obtained, and an aqueous dispersion having excellent dispersion stability can be obtained. In addition, by precipitating the aqueous dispersion, polytetrafluoroethylene powder can be recovered, and it is difficult for polytetrafluoroethylene (unprecipitated polymer) to remain in the wastewater remaining after the powder is recovered.

[0088] The above PTFE contains 99.0 mass% or more of polymerization units based on TFE and 1.0 mass% or less of polymerization units based on the modified monomer. Such PTFE is also referred to as modified PTFE.

[0089] In the above PTFE, the content of the polymerization unit based on the modifying monomer (also denoted as "modifying monomer unit" hereinafter) is preferably in the range of 0.00001% by mass to 1.0% by mass relative to all the polymerization units of PTFE. As the lower limit of the content of the modifying monomer unit, it is more preferably 0.0001% by mass, still more preferably 0.0005% by mass, further preferably 0.001% by mass, still further preferably 0.005% by mass, particularly preferably 0.009% by mass. As the upper limit of the content of the modifying monomer unit, it is preferably 0.90% by mass, more preferably 0.50% by mass, further preferably 0.40% by mass, still further preferably 0.30% by mass, especially more preferably 0.10% by mass, particularly preferably 0.08% by mass, particularly preferably 0.05% by mass, more preferably 0.01% by mass.

[0090] In this specification, the above-mentioned modifying monomer unit refers to the part derived from the modifying monomer that is a part of the molecular structure of PTFE.

[0091] In this specification, the content of each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

[0092] As the above-mentioned modifying monomer, there is no particular limitation as long as it can copolymerize with TFE, and fluorine-containing monomers and non-fluorine-containing monomers can be cited. In addition, the modifying monomer used may be one kind or two or more kinds.

[0093] There is no particular limitation on the non-fluorine-containing monomer, and the general formula:

[0094] CH2=CR Q1 -LR Q2

[0095] (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) the monomer shown.

[0096] As the non-fluorine-containing 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-fluorine-containing monomer, among them, butyl methacrylate, vinyl acetate, and acrylic acid are preferred.

[0097] As the fluorine-containing monomer, perfluoroolefins such as hexafluoropropylene [HFP] can be mentioned; hydrogen-containing fluorinated olefins such as trifluoroethylene and vinylidene fluoride [VDF]; perhaloolefins such as chlorotrifluoroethylene; perfluoroethylene ethers; (perfluoroalkyl)ethylenes, etc.

[0098] As the above-mentioned perfluoroethylene ether, there is no particular limitation, and for example, the following general formula (A) can be mentioned:

[0099] CF2=CF-ORf(A)

[0100] (In the formula, Rf represents a perfluoroorganic group) and other perfluoro unsaturated compounds. In the present specification, the above-mentioned "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The above-mentioned perfluoroorganic group may have an ether oxygen.

[0101] As the above-mentioned perfluoroethylene ether, for example, perfluoro(alkyl vinyl ether) [PAVE] in which Rf in the above general formula (A) is a perfluoroalkyl group having 1 to 10 carbon atoms can be mentioned. The number of carbon atoms of the above-mentioned perfluoroalkyl group is preferably 1 to 5.

[0102] As the perfluoroalkyl group in the above-mentioned PAVE, for example, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, etc. can be mentioned.

[0103] As the above-mentioned perfluoroethylene ether, further, monomers in which Rf in the above general formula (A) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, monomers in which Rf is the following formula:

[0104] [Chemical formula 1]

[0105]

[0106] (In the formula, m represents an integer of 0 or 1 to 4), monomers in which Rf is the following formula:

[0107] [Chemical formula 2]

[0108]

[0109] (In the formula, n represents an integer of 1 to 4), and other monomers.

[0110] As the hydrogen-containing fluorinated olefin, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E isomer), CHF=CHCF3 (Z isomer), etc. can be mentioned.

[0111] As the (perfluoroalkyl)ethylene (PFAE), there is no particular limitation, and examples thereof include (perfluorobutyl)ethylene (PFBE), (perfluorohexyl)ethylene, and the like.

[0112] As the above-mentioned modified monomer, a modified monomer (3) having a monomer reactivity ratio of 0.1 to 8 is also preferably exemplified. By the presence of the modified monomer (3), PTFE particles with a small particle size can be obtained, and an aqueous dispersion with high dispersion stability can be obtained.

[0113] 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 modified monomer is the above-mentioned monomer reactivity ratio. The lower this value, the higher the reactivity of the modified monomer with TFE. The monomer reactivity ratio can be calculated as follows: copolymerize TFE and the modified monomer, determine the composition in the resulting polymer at the beginning, and calculate it from the Fineman-Ross equation.

[0114] The above copolymerization is carried out in a 6.0 L stainless steel autoclave using 3600 g of deionized and degassed water, ammonium perfluorooctanoate at 1000 ppm 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 modified monomer are respectively added to the reactor, 0.072 g of ammonium persulfate (20 ppm relative to water) is added, and TFE is continuously supplied to maintain a polymerization pressure of 0.78 MPa. When the TFE feed amount reaches 1000 g, stirring is stopped, and the pressure is released until the reactor reaches atmospheric pressure. After cooling, the paraffin is separated, and an aqueous dispersion containing the resulting polymer is thus obtained. The above aqueous dispersion is stirred to precipitate the resulting polymer, and dried at 150 °C. The composition in the resulting polymer is calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis according to the type of monomer.

[0115] As the modified monomer (3) having a monomer reactivity ratio of 0.1 to 8, at least one selected from the group consisting of modified monomers represented by formulas (3a) to (3d) is preferred.

[0116] CH2=CH-Rf 1 (3a)

[0117] (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms.)

[0118] CF2=CF-O-Rf 2 (3b)

[0119] (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 2 carbon atoms.)

[0120] CF2=CF-O-(CF2) n CF=CF2(3c)

[0121] (In the formula, n is 1 or 2.)

[0122] [Chemical formula 3]

[0123]

[0124] (In the formula, X 3 and X 4 are F, Cl or methoxy group, and Y is of formula Y1 or Y2.)

[0125] [Chemical formula 4]

[0126] -CF=CF- (Y1)

[0127]

[0128] (In formula Y2, Z and Z' are F or a fluoroalkyl group having 1 to 3 carbon atoms.)

[0129] The content of the modified monomer (3) unit is preferably in the range of 0.00001% by mass to 1.0% by mass relative to all the polymerization units of PTFE. As the lower limit, it is more preferably 0.0001% by mass, still more preferably 0.0005% by mass, further preferably 0.001% by mass, still further preferably 0.005% by mass, particularly preferably 0.009% by mass. As the upper limit, it is preferably 0.90% by mass, more preferably 0.50% by mass, further preferably 0.40% by mass, still further preferably 0.30% by mass, especially more preferably 0.10% by mass, particularly preferably 0.08% by mass, particularly preferably 0.05% by mass, more preferably 0.01% by mass.

[0130] As the above-mentioned modified monomer, since an aqueous dispersion having a small average primary particle diameter of the modified polytetrafluoroethylene particles, a small aspect ratio of the primary particles, and excellent 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, an aqueous dispersion of PTFE having a smaller average primary particle diameter, a small aspect ratio of the primary particles, and excellent dispersion stability can be obtained. In addition, an aqueous dispersion with less precipitated polymer can be obtained.

[0131] From the aspect of reactivity with TFE, the above-mentioned modified monomer preferably contains at least one selected from the group consisting of hexafluoropropene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene.

[0132] More preferably, it contains at least one selected from the group consisting of hexafluoropropene, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), (perfluorobutyl)ethylene, (perfluorohexyl)ethylene, and (perfluorooctyl)ethylene.

[0133] The total amount of the above-mentioned hexafluoropropene unit, perfluoro(alkyl vinyl ether) unit, and (perfluoroalkyl)ethylene unit is preferably in the range of 0.00001% by mass to 1% by mass with respect to all the polymerization units of PTFE. As the lower limit of the above total amount, it is more preferably 0.0001% by mass, further preferably 0.0005% by mass, still further preferably 0.001% by mass, still further preferably 0.005% by mass, and particularly preferably 0.009% by mass. As the upper limit, it is more preferably 0.50% by mass, further preferably 0.40% by mass, still further preferably 0.30% by mass, especially more preferably 0.10% by mass, particularly preferably 0.08% by mass, particularly preferably 0.05% by mass, and more preferably 0.01% by mass.

[0134] The above-mentioned 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)").

[0135] By the presence of the above-mentioned modified monomer (A), PTFE particles with a small primary particle size can be obtained, and an aqueous dispersion with high dispersion stability can be obtained. In addition, the amount of unprecipitated polymer can be reduced. Furthermore, the aspect ratio of the primary particles can be reduced.

[0136] The amount of the above-mentioned modified monomer (A) is preferably an amount exceeding the amount equivalent to 0.1 ppm in the aqueous medium, more preferably an amount exceeding 0.5 ppm, further preferably an amount exceeding 1.0 ppm, still further preferably 5 ppm or more, and particularly preferably 10 ppm or more. If the amount of the above-mentioned modified monomer (A) is too small, the average primary particle size of the obtained PTFE may not be reduced.

[0137] The amount of the above-mentioned modified monomer (A) may be within the above range. For example, the upper limit can be 5000 ppm. In addition, in the above manufacturing method, in order to improve the stability of the aqueous dispersion during or after the reaction, the modified monomer (A) can be added to the system during the reaction.

[0138] The above-mentioned modified monomer (A) has high water solubility. Therefore, even if the unreacted modified monomer (A) remains in the aqueous dispersion, it is easily removed in the concentration step or the precipitation / washing step.

[0139] The above-mentioned modified monomer (A) is introduced into the polymer during the polymerization process. However, since the concentration of the modified monomer (A) in the polymerization system is low by itself and the amount introduced into the polymer is small, there is no problem of reduction in the heat resistance of PTFE or coloring after firing.

[0140] Examples of the hydrophilic group in the above-mentioned modified monomer (A) include, for example, -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7y 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7y is H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring). Among the above-mentioned hydrophilic groups, -SO3M or -COOM is preferred. As the R 7y in the organic group, an alkyl group is preferred. As R 7y , H or C 1-10 of the organic group is preferred, more preferably H or C 1-4 of the organic group, further preferably H or C 1-4 of the alkyl group.

[0141] Examples of the above-mentioned metal atom include monovalent and divalent metal atoms, and examples include alkali metals (Group 1), alkaline earth metals (Group 2), etc. Na, K, or Li is preferred.

[0142] Examples of the "functional group capable of reacting in radical polymerization" in the above-mentioned 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:

[0143] CX e X g =CX f R-

[0144] (wherein X e , X f and X g are each independently F, Cl, H, CF3, CF2H, CFH2, or CH3; R is a linking group). Examples of the linking group for R include R aPreferred examples include groups having unsaturated bonds such as -CH=CH2, -CF=CH2, -CH=CF2, -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-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.

[0145] Since the modified monomer (A) has a functional group that can react in free radical polymerization, it is presumed that if used in the polymerization, it reacts with the fluorinated monomer in the initial stage of the polymerization reaction, and has a hydrophilic group derived from the modified monomer (A), and can form particles with high stability. Therefore, it is believed that if the polymerization is carried out in the presence of the modified monomer (A), the number of particles increases.

[0146] In the above polymerization, the above-mentioned modified monomer (A) may be present alone or in combination of two or more.

[0147] In the above-mentioned polymerization, a compound having an unsaturated bond can be used as the above-mentioned modified monomer (A).

[0148] The modified monomer (A) is preferably of the general formula (4):

[0149] CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4)

[0150] (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).

[0151] As the above hydrophilic group, for example, -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (in each formula, M is H, a metal atom, NR 7y 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 7y is H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring). As the above hydrophilic group, -SO3M or -COOM is preferred. As the organic group in R 7y , an alkyl group is preferred. As R 7y , H or a C 1-10 organic group is preferred, more preferably H or a C 1-4 organic group, still more preferably H or a C 1-4 alkyl group. 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.

[0152] By using the above modified monomer (A), an aqueous dispersion with a smaller average primary particle size and more excellent stability can be obtained. In addition, the aspect ratio of the primary particles can be further reduced.

[0153] The above R a is a linking group. In this specification, 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 upper limit, for example, it can be 100 or less, and can also be 50 or less.

[0154] 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.

[0155] The above R a is preferably a linear heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0156] R a In the case of being a divalent organic group, the hydrogen atom bonded to the carbon atom can be substituted by a halogen other than fluorine, such as chlorine, and can contain or not contain a double bond. In addition, R aIt can be either linear or branched, and can also be either cyclic or acyclic. Additionally, R a can contain functional groups (such as esters, ethers, ketones, amines, halides, etc.).

[0157] Additionally, R a can be a divalent organic group that is non-fluorinated, or a partially fluorinated or perfluorinated divalent organic group.

[0158] 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 oxygen atoms, may contain double bonds, and may also contain functional groups.

[0159] R a is preferably a hydrocarbon group with 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.

[0160] As R a , it is 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.

[0161] In the formula, a, b, c, and d are each independently at least 1 or more. a, b, c, and d can each 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.

[0162] As R aPreferable 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-.

[0163] In the above formula, n is an integer from 1 to 10.

[0164] As -R in the above general formula (4) 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-.

[0165] In the above formula, n is an integer from 1 to 10.

[0166] As a specific example of the compound represented by the general formula (4), there can be cited

[0167] [Chemical Formula 5]

[0168]

[0169] (In the formula, X j and Y 3 are the same as above. n is an integer from 1 to 10) etc.

[0170] As R a , the following general formula (r1) is preferred:

[0171] -(C=O) h -(O) i- CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -(r1)

[0172] (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, and the following general formula (r2) is also preferred:

[0173] -(C=O) h -(O) i- CF2-O-(CX 7 2) e -(O) g -(r2)

[0174] (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.

[0175] As -R in the above general formula (4) a -(CZ 1 Z 2 ) k -, and the following formula (t1) is also preferred:

[0176] -(C=O) h -(O) i- CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 -(t1)

[0177] (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.

[0178] In addition, in the above general formula (4), as -R a -(CZ 1 Z 2 ) k -, and the following formula (t2) is also preferred:

[0179] -(C=O) h -(O) i- CF2-O-(CX 7 2) e -(O) g -CZ1 Z 2 -(t2)

[0180] (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, and Z 1 and Z 2 are each independently a divalent group represented by H, F or CF3). In formula (t2), Z 1 and Z 2 are more preferably one is F and the other is CF3.

[0181] The compound represented by the general formula (4) 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 the general formula (4), it is preferred that X i , X j and X k are all F, and 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 linear heteroatom. The number of carbon atoms of the above perfluoroalkylene group can be 2 to 20, or can be 4 to 18.

[0182] The compound represented by the general formula (4) can also be partially fluorinated. That is, the compound represented by the general formula (4) 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 ).

[0183] The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4a).

[0184] CF2=CF-O-Rf 0 -Y 3 (4a)

[0185] (wherein Y 3 is a hydrophilic group, and 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).

[0186] The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4b).

[0187] CH2=CH-O-Rf 0 -Y 3 (4b)

[0188] (wherein, Y 3 is a hydrophilic group, and Rf 0 is a perfluorinated divalent linking group defined by formula (4a).)

[0189] In general formula (4), Y 3 being -OSO3M is one of the preferred embodiments. When Y 3 is -OSO3M, examples of the compound represented by general formula (4) 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.

[0190] In general formula (4), Y 3 being -SO3M is also one of the preferred embodiments. When Y 3 is -SO3M, examples of the compound represented by general formula (4) 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)4SO3M), etc. In the above formulas, M is the same as described above.

[0191] In general formula (4), Y 3 being -COOM is also one of the preferred embodiments. When Y 3When it is -COOM, as the compound represented by the general formula (4), 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)4COOM), CF2=CF(OCF2CF2SO2NR’CH2COOM), CF2=CF(O(CF2)4SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)SO2NR’CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR’CH2COOM),

[0192]

[0193] CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR’CH2COOM),

[0194] CH2=CH((CF2)4SO2NR’CH2COOM), CH2=CH(CF2CF2SO2NR’CH2COOM),

[0195] CH2=CH((CF2)4SO2NR’CH2COOM) etc. In the above formula, R’ is H or C 1-4 alkyl group, and M is the same as above.

[0196] In the general formula (4), Y 3 being -OPO3M is also one of the preferred modes. When Y 3When it is -OPO3M, as the compound represented by the general formula (4), 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)4CH2OP(O)(OM)2), etc. In the above formula, M is the same as described above.

[0197] In the general formula (4), Y 3 being -PO3M is also one of the preferred modes. When Y 3 is -PO3M, as the compound represented by the general formula (4), 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)4P(O)(OM)2), etc. In the formula, M is the same as described above.

[0198] As the compound represented by the above general formula (4), it is preferably at least one selected from the group consisting of the following monomers, and the monomer is the following general formula (5):

[0199] CX2=CY(-CZ2-O-Rf-Y 3 )(5)

[0200] (In the formula, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, Z is the same or different and is -H, -F, an alkyl group or a fluorinated alkyl 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. Y 3The monomer shown above (the same as above).) The monomer represented by the following general formula (6):

[0201] CX2=CY(-O-Rf-Y 3 ) (6)

[0202] (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, 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. Y 3 The monomer shown above (the same as above); and the following general formula (7):

[0203] CX2=CY(-Rf-Y 3 ) (7)

[0204] (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, 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. Y 3 The monomer shown above (the same as above).

[0205] It should be noted that the fluoroalkylene group having an ether bond and 2 to 100 carbon atoms mentioned above is an alkylene group that does not contain a structure with an oxygen atom at the end but contains an ether bond between carbon atoms.

[0206] In the above general formula (5), X is -H or -F. X can be both -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.

[0207] In the above general formula (5), Y is -H, -F, an alkyl group or a fluoroalkyl group.

[0208] The above alkyl group is an alkyl group that does not contain a fluorine atom 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.

[0209] The above fluoroalkyl group is an alkyl group that contains 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.

[0210] As the above Y, -H, -F or -CF3 is preferred, and -F is more preferred.

[0211] In the above general formula (5), Z is the same or different and is -H, -F, an alkyl group or a fluoroalkyl group.

[0212] The above alkyl group is an alkyl group that does not contain a fluorine atom 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.

[0213] The above-mentioned fluoroalkyl group is an alkyl group containing at least 1 fluorine atom, and the number of carbon atoms may be 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 further preferably 3 or less.

[0214] As the above-mentioned Z, -H, -F or -CF3 is preferred, and -F is more preferred.

[0215] In the above general formula (5), 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.

[0216] In the above general formula (5), 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.

[0217] 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 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.

[0218] The number of carbon atoms of the above-mentioned 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 further preferably 12 or less.

[0219] As the fluoroalkylene group having an ether bond, for example, the following formula is also preferred:

[0220] [Chemical formula 6]

[0221]

[0222] (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.

[0223] Specific examples of the above-mentioned fluoroalkylene group having an ether bond include -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n-CF(CF3)-(wherein 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.

[0224] In the above general formula (5), Y 3 is -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7y 4, imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R 7y 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).

[0225] As the organic group in R 7y is preferably an alkyl group.

[0226] As R 7y is preferably H or C 1-10 of an organic group, more preferably H or C 1-4 of an organic group, further preferably H or C 1-4 of an alkyl group.

[0227] As the above metal atom, examples include alkali metals (Group 1), alkaline earth metals (Group 2), etc., and preferably Na, K or Li.

[0228] As the above M, it is preferably -H, a metal atom or -NR 7y 4, more preferably -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7y 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.

[0229] As the above Y 3 is preferably -COOM or -SO3M, more preferably -COOM.

[0230] The monomer represented by the general formula (5) is preferably the monomer (5a) represented by the following general formula (5a).

[0231] CH2=CF(-CF2-O-Rf-Y 3 )(5a)

[0232] (wherein, Rf and Y 3 are the same as described above.)

[0233] As the monomer represented by the general formula (5a), specifically, the following formula can be exemplified

[0234] [Chemical Formula 7]

[0235]

[0236] (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 of 0 to 10; s1 is 0 or 1; t1 is an integer of 0 to 5, and Y 3 is the same as described above. Among them, when both Z 3 and Z 4 are H, p1 + q1 + r1 + s1 is not 0) of the monomer. More specifically, preferably, the following can be exemplified

[0237] [Chemical Formula 8]

[0238]

[0239] CH2 = CFCF2OCH2CF2 - Y 3 , CH2 = CFCF2O(CH2CF2CF2O)CH2CF2 - Y 3 ,

[0240] CH2 = CFCF2OCH2CF2CH2 - Y 3 ,

[0241] CH2 = CFCF2O(CH2CF2CF2O)CH2CF2CH2 - Y 3 ,

[0242] CH2 = CFCF2OCF2CF2 - Y 3 , CH2 = CFCF2O(CF2CF2CF2O)CF2CF2 - Y 3 ,

[0243] CH2 = CFCF2OCF2CF2CH2 - Y 3 ,

[0244] CH2 = CFCF2O(CF2CF2CF2O)CF2CF2CH2 - Y 3 ,

[0245] CH2 = CFCF2OCF2 - Y 3, CH2=CFCF2O(CF2CF2O)CF2-Y 3 ,

[0246] CH2=CFCF2OCF2CH2-Y 3 ,

[0247] CH2=CFCF2O(CF2CF2O)CF2CH2-Y 3 ,

[0248] etc., and preferably

[0249] [Chemical Formula 9]

[0250]

[0251] As the monomer represented by the above general formula (5a), Y in the formula (5a) is preferably 3 -COOM, and particularly preferably at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein, M is the same as defined above), and more preferably CH2=CFCF2OCF(CF3)COOM.

[0252] The monomer represented by the general formula (5) is preferably the monomer (5b) represented by the following general formula (5b).

[0253] CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5b)

[0254] (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 the same as defined above.)

[0255] In the above formula (5b), from the aspect of the stability of the obtained aqueous dispersion, the above 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 aspect of obtaining appropriate water solubility and the stability of the aqueous dispersion, the above Y 3 is preferably -COOM 1 , and from the aspect that it is difficult to remain as an impurity and the heat resistance of the obtained molded body is improved, the above M 1 is preferably H or NH4.

[0256] As the perfluoro vinyl alkyl compound represented by the above formula (5b), for example, CH2=CFCF2OCF(CF3)COOM can be cited 1, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM 1 (wherein M 1 is as defined above).

[0257] In addition, as the monomer represented by the general formula (5), monomers represented by the following general formula (5c) etc. can also be cited.

[0258] CF2=CFCF2-O-Rf-Y 3 (5c)

[0259] (wherein Rf and Y 3 are the same as above.)

[0260] More specifically, examples include

[0261] [Chemical formula 10]

[0262] CF2=CFCF2OCF2CF2CF2-Y 3 ,

[0263]

[0264] CF2=CFCF2OCF2CF2CF2CH2-Y 3 ,

[0265] etc.

[0266] In the above general formula (6), X is -H or -F. X can be both -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.

[0267] In the above general formula (6), Y is -H, -F, an alkyl group or a fluoroalkyl group.

[0268] 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.

[0269] 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.

[0270] As the above Y, -H, -F or -CF3 is preferred, and -F is more preferred.

[0271] In the above general formula (6), 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.

[0272] In the above general formula (6), 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.

[0273] The number of carbon atoms of the above fluoroalkylene group is preferably 2 or more. In addition, the number of carbon atoms of the 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.

[0274] The monomer represented by the above general formula (6) is preferably at least one selected from the group consisting of monomers represented by the following general formulas (6a), (6b), (6c), (6d) and (6e).

[0275] CF2=CF-O-(CF2) n1 -Y 3 (6a)

[0276] (In the formula, n1 represents an integer of 1 to 10, and Y 3 represents -SO3M 1 or -COOM 1 , M 1 represents H, a metal atom, NR 7y 4, imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, and R 7y represents H or an organic group.)

[0277] CF2=CF-O-(CF2C(CF3)F) n2 -Y 3 (6b)

[0278] (In the formula, n2 represents an integer of 1 to 5, and Y 3 has the same definition as above.)

[0279] CF2=CF-O-(CFX 1 ) n3 -Y 3 (6c)

[0280] (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, and Y 3 has the same definition as above.)

[0281] CF2=CF-O-(CF2CFX 1 O) n4-CF2CF2-Y 3 (6d)

[0282] (In the formula, n4 represents an integer from 1 to 10, and Y 3 and X 1 are as defined above.)

[0283] CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-Y 3 (6e)

[0284] (In the formula, n5 represents an integer from 0 to 10, and Y 3 and X 1 are as defined above.)

[0285] In the above formula (6a), 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 stability of the aqueous dispersion, the above Y 3 is preferably -COOM 1 , and from the aspect of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M 1 is preferably H or NH4.

[0286] As the monomer represented by the above formula (6a), for example, CF2=CF-O-CF2COOM 1 (In the formula, M 1 is as defined above) can be cited.

[0287] In the above formula (6b), from the aspect of the stability of the obtained aqueous dispersion, the above n2 is preferably an integer of 3 or less, and from the aspect of obtaining moderate water solubility and stability of the aqueous dispersion, Y 3 is preferably -COOM 1 , and from the aspect of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M 1 is preferably H or NH4.

[0288] In the above formula (6c), from the aspect of water solubility, the above n3 is preferably an integer of 5 or less, and from the aspect of obtaining moderate water solubility and stability of the aqueous dispersion, the above Y 3 is preferably -COOM 1 , and from the aspect of improving dispersion stability, the above M 1 is preferably H or NH4.

[0289] In the above formula (6d), from the aspect of the stability of the aqueous dispersion, the above X 1Preferably -CF3. From the aspect of water solubility, n4 above is preferably an integer of 5 or less. From the aspect of obtaining appropriate water solubility and the stability of the aqueous dispersion, Y above 3 is preferably -COOM 1 , M above 1 is preferably H or NH4.

[0290] As the monomer represented by the above formula (6d), for example, CF2=CFOCF2CF(CF3)OCF2CF2COOM can be cited 1 (wherein, M 1 represents H, NH4 or an alkali metal).

[0291] In the general formula (6e), from the aspect of water solubility, n5 above is preferably an integer of 5 or less. From the aspect of obtaining appropriate water solubility and the stability of the aqueous dispersion, Y above 3 is preferably -COOM 1 , M above 1 is preferably H or NH4.

[0292] As the monomer represented by the general formula (6e), for example, CF2=CFOCF2CF2CF2COOM can be cited 1 (wherein, M 1 represents H, NH4 or an alkali metal).

[0293] In the above general formula (7), Rf is preferably a fluoroalkylene having 1 to 40 carbon atoms. In the general formula (7), at least one of X and Y preferably contains a fluorine atom.

[0294] The monomer represented by the above general formula (7) is preferably selected from the following general formula (7a):

[0295] CF2=CF-(CF2) n1 -Y 3 (7a)

[0296] (wherein, n1 represents an integer of 1 to 10, and Y 3 has the same definition as above) and the following general formula (7b):

[0297] CF2=CF-(CF2C(CF3)F) n2 -Y 3 (7b)

[0298] (wherein, n2 represents an integer of 1 to 5, and Y 3 has the same definition as above) and at least one selected from the group consisting of the monomers represented thereby.

[0299] Y above 3 is preferably -SO3M 1or -COOM 1 , M 1 is preferably H, a metal atom, NR 7y 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents. The above R 7y represents H or an organic group.

[0300] In the above 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 the stability of the aqueous dispersion, the above Y 3 is preferably -COOM 1 , and from the aspect of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M 1 is preferably H or NH4.

[0301] Examples of the perfluoro vinyl alkyl compound represented by the above formula (7a) include CF2=CFCF2COOM 1 (wherein, M 1 is the same as the above definition).

[0302] In the above formula (7b), from the aspect of the stability of the obtained aqueous dispersion, the above n2 is preferably an integer of 3 or less, and from the aspect of obtaining moderate water solubility and the stability of the aqueous dispersion, Y 3 is preferably -COOM 1 , and from the aspect of being difficult to remain as an impurity and improving the heat resistance of the obtained molded body, M 1 is preferably H or NH4.

[0303] The above modified monomer preferably contains modified monomer (A), preferably contains at least one selected from the group consisting of the compounds represented by general formula (5c), general formula (6a), general formula (6b), general formula (6c), and general formula (6d), and more preferably contains the compound represented by general formula (5c).

[0304] When the above-mentioned modified monomer contains the above-mentioned modified monomer (A), the content of the polymerization unit based on the modified monomer (A) is preferably in the range of 0.00001% by mass to 1.0% by mass relative to all the polymerization units of PTFE. As the lower limit, it is more preferably 0.0001% by mass, still more preferably 0.0005% 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, it is preferably 0.90% by mass, more preferably 0.50% by mass, further preferably 0.40% by mass, still further preferably 0.30% by mass, particularly more preferably 0.10% by mass, particularly preferably 0.08% by mass, particularly preferably 0.05% by mass, and more preferably 0.01% by mass.

[0305] The above-mentioned PTFE may have a core-shell structure. The above-mentioned core-shell structure is a structure well-known in the art and is the structure of primary particles in an aqueous dispersion that can be manufactured by methods described in, for example, the specification of U.S. Patent No. 6,841,594.

[0306] Examples of polytetrafluoroethylene having a core-shell structure include a core-shell structure in which the core part contains a TFE homopolymer and the shell part contains a modified PTFE, a core-shell structure in which the core part contains a modified PTFE and the shell part contains a TFE homopolymer, and a core-shell structure in which the core part contains a modified PTFE and the shell part contains a modified PTFE having a monomer composition different from that of the modified PTFE constituting the core part.

[0307] The above-mentioned PTFE having a core-shell structure can be obtained, for example, as follows: First, TFE and, if necessary, a modified monomer are polymerized to produce the core part (TFE homopolymer or modified PTFE), and then TFE and, if necessary, a modified monomer are polymerized to produce the shell part (TFE homopolymer or modified PTFE).

[0308] The above-mentioned shell part refers to the part that constitutes a specified thickness from the surface of the PTFE primary particle toward the particle interior, and the core part refers to the part that constitutes the interior of the shell part.

[0309] In this specification, the above-mentioned core-shell structure includes all of the following cases: (1) the case where the core part and the shell part have different monomer compositions; (2) the case where the core part and the shell part have the same monomer composition and the number-average molecular weights of the two parts are different; (3) the case where the core part and the shell part have different monomer compositions and the number-average molecular weights of the two parts are also different.

[0310] When the shell part is made of modified PTFE, the content of the modifying monomer in the shell part is preferably 0.00001% by mass to 1.0% by mass. More preferably, it is 0.0001% by mass or more, further preferably 0.001% by mass or more, and still more preferably 0.01% by mass or more. In addition, it is more preferably 0.50% by mass or less, and further preferably 0.30% by mass or less.

[0311] When the core part is made of modified PTFE, the content of the modifying monomer in the core part is preferably 0.00001% by mass to 1.0% by mass. More preferably, it is 0.0001% by mass or more, and further preferably 0.001% by mass or more. In addition, it is more preferably 0.50% by mass or less, and further preferably 0.30% by mass or less.

[0312] The average primary particle diameter of the above-mentioned PTFE is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 350 nm or less. By the manufacturing method of the present invention, PTFE with a small average primary particle diameter can be obtained. The lower limit of the average primary particle diameter is not particularly limited. For example, it can be 50 nm or 100 nm. From the aspect of molecular weight, for example, in the case of high molecular weight PTFE, it is preferably 100 nm or more, and more preferably 150 nm or more.

[0313] The above-mentioned average primary particle diameter can be measured by the dynamic light scattering method. Regarding the above-mentioned average primary particle diameter, a PTFE aqueous dispersion with a solid component concentration adjusted to about 1.0% by mass is prepared, and the dynamic light scattering method can be used to measure it under the conditions of 25 °C, the refractive index of the solvent (water) being 1.3328, the viscosity of the solvent (water) being 0.8878 mPa·s, and accumulating 70 times. As the dynamic light scattering method, for example, ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) can be used.

[0314] The aspect ratio of the primary particles of the above-mentioned PTFE is preferably 1.45 or less. The aspect ratio is more preferably 1.40 or less, further preferably 1.35 or less, still more preferably 1.30 or less, particularly preferably 1.25 or less, especially preferably 1.20 or less, and particularly especially preferably 1.15 or less.

[0315] In the case of measurement in an aqueous dispersion, the aspect ratio is obtained as follows: The PTFE aqueous dispersion with a solid component concentration diluted to about 1 mass% is observed by 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. In the case of measurement using powder, the aspect ratio is obtained as follows: After irradiating the PTFE powder with electron rays, it is added to an aqueous solution of a fluorosurfactant and redispersed using ultrasonic waves, whereby a PTFE aqueous dispersion can be obtained. From this PTFE aqueous dispersion, the aspect ratio is obtained by the same method as the method for measurement by the above aqueous dispersion.

[0316] The standard specific gravity (SSG) of the above PTFE is preferably 2.280 or less, more preferably 2.200 or less, further preferably 2.190 or less, and still more preferably 2.180 or less. In addition, it is preferably 2.130 or more. The above SSG is measured by the water displacement method according to ASTM D-792 using a sample molded according to ASTM D4895-89.

[0317] The thermal instability index (TII) of the above PTFE can be 20 or more. This PTFE is obtained by using a hydrocarbon surfactant. The TII is preferably 25 or more, more preferably 30 or more, further preferably 35 or more. Particularly preferably, it is 40 or more. The above TII is measured according to ASTM D 4895-89.

[0318] The 0.1% weight loss temperature of the above PTFE can be 400 °C or less. This PTFE is obtained by using a hydrocarbon surfactant. The above 0.1% weight loss temperature is a value measured by the following method.

[0319] Accurately weigh about 10 mg of PTFE powder that has not been heated to a temperature above 300 °C, place it in a dedicated aluminum pan, and measure it using TG / DTA (simultaneous differential thermal and thermogravimetric analyzer). Regarding the 0.1% weight loss temperature, in an air atmosphere, in the temperature range of 25 °C to 600 °C, the aluminum pan is heated at a rate of 10 °C / minute, and the temperature corresponding to the point where the weight decreases by 0.1 mass% is taken as the 0.1% weight loss temperature.

[0320] The 1.0% weight loss temperature of the above PTFE can be 492 °C or less. This PTFE is obtained by using a hydrocarbon surfactant. The above 1.0% weight loss temperature is a value measured by the following method.

[0321] Precisely weigh approximately 10 mg of PTFE powder that has not been heated to a temperature above 300 °C, place it in a dedicated aluminum dish, and perform measurements using TG / DTA (simultaneous differential thermal and thermogravimetric analyzer). Regarding the 1.0% weight loss temperature, under an air atmosphere, in the temperature range from 25 °C to 600 °C, heat the aluminum dish at a rate of 10 °C / minute, and take the temperature corresponding to the point where the weight has decreased by 1.0% as the 1.0% weight loss temperature.

[0322] The peak temperature of the above-mentioned PTFE is preferably 342 °C or lower, more preferably 341 °C or lower, and even more preferably 340 °C or lower. The above peak temperature is the value measured by the following method.

[0323] Precisely weigh approximately 10 mg of powder that has not been heated to a temperature above 300 °C, place it in a dedicated aluminum dish, and perform measurements using TG / DTA (simultaneous differential thermal and thermogravimetric analyzer). Regarding the peak temperature, under an air atmosphere, in the temperature range from 25 °C to 600 °C, heat the aluminum dish at a rate of 10 °C / minute, and take the temperature corresponding to the maximum value of the differential thermal (DTA) curve as the peak temperature.

[0324] The extrusion pressure of the above-mentioned PTFE is preferably 50.0 MPa or lower, more preferably 40.0 MPa or lower, preferably 5.0 MPa or higher, more preferably 10.0 MPa or higher, and even more preferably 15.0 MPa or higher. The above extrusion pressure is the value obtained by the following method.

[0325] Add 21.7 g of a lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon Corporation) to 100 g of PTFE powder, and mix in a glass bottle at room temperature for 3 minutes. Next, before extrusion, leave the glass bottle at room temperature (25 °C) for at least 1 hour to obtain a lubricated resin. Pass the lubricated resin through a hole (diameter 2.5 mm, land length 11 mm, lead angle 30°), and perform paste extrusion at room temperature with a reduction ratio of 100:1 to obtain uniform beads (beading; extrusion molded body). The extrusion speed, i.e., the stamping speed, is set to 20 inches / minute (51 cm / minute). The extrusion pressure is the value obtained as follows: Measure the load when the extrusion load reaches a balanced state during paste extrusion, divide it by the cross-sectional area of the barrel used in paste extrusion, and take the resulting value as the extrusion pressure.

[0326] The above-mentioned PTFE generally has stretchability, fibrillating properties, and non-melting secondary processability.

[0327] The above-mentioned non-melting secondary processability refers to the property that the melt flow rate cannot be measured at a temperature above the crystallization melting point according to ASTM D-1238 and D-2116, that is, the property of not being easily flowable even in the melting temperature range.

[0328] The production method of the present invention includes a polymerization step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant to obtain polytetrafluoroethylene.

[0329] In the above polymerization step, the polymerization temperature and polymerization pressure are appropriately determined according to the types of monomers used, the molecular weight of the target PTFE, and the reaction rate.

[0330] For example, the polymerization temperature is preferably 10°C to 150°C. The polymerization temperature is more preferably 30°C or higher, further preferably 50°C or higher. In addition, it is more preferably 120°C or lower, further preferably 100°C or lower.

[0331] The polymerization pressure is preferably 0.05 MPa to 10 MPa. The polymerization pressure is more preferably 0.3 MPa or higher, further preferably 0.5 MPa or higher. In addition, it is more preferably 5.0 MPa or lower, further preferably 3.0 MPa or lower. In particular, from the aspect of increasing the yield of PTFE, it is preferably 1.0 MPa or higher, more preferably 1.2 MPa or higher, still more preferably 1.5 MPa or higher, especially more preferably 1.8 MPa or higher, and particularly preferably 2.0 MPa or higher.

[0332] In the above polymerization step, the amount of the hydrocarbon surfactant at the start of polymerization exceeds 50 ppm relative to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or higher, more preferably 70 ppm or higher, further preferably 80 ppm or higher, still more preferably 100 ppm or higher, especially further preferably 150 ppm or higher, particularly preferably 200 ppm or higher, and most preferably 300 ppm or higher. The upper limit is not particularly limited. For example, it is preferably 10000 ppm, more preferably 5000 ppm. By making the amount of the hydrocarbon surfactant at the start of polymerization within the above range, an aqueous dispersion with a smaller average primary particle size and more excellent stability can be obtained. In addition, an aqueous dispersion with a smaller amount of un-precipitated polymer can be obtained. Furthermore, the aspect ratio of the primary particles can be further reduced.

[0333] The polymerization can start when the gaseous fluoromonomer in the reactor becomes polytetrafluoroethylene and the pressure in the reactor decreases. U.S. Patent No. 3,391,099 (Punderson) discloses the dispersion polymerization of tetrafluoroethylene 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. In addition, in the present invention, an additive related to the formation of nucleation sites is used as a nucleating agent.

[0334] The above polymerization step is a step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant. In the above step, a step of continuously adding a hydrocarbon surfactant is also preferably included.

[0335] The continuous addition of the hydrocarbon surfactant means, for example, adding the hydrocarbon surfactant not all at once but over time without interruption or in batches.

[0336] In the step of continuously adding the hydrocarbon surfactant, it is preferred to start adding the hydrocarbon surfactant to the aqueous medium when the concentration of PTFE formed in the aqueous medium is less than 0.60% by mass. The above hydrocarbon surfactant is more preferably started to be added when the concentration is 0.50% by mass or less, further preferably when the concentration is 0.36% by mass or less, still more preferably when the concentration is 0.30% by mass or less, particularly more preferably when the concentration is 0.20% by mass or less, especially preferably when the concentration is 0.10% by mass or less, and most preferably started to be added simultaneously with the start of polymerization. The above concentration is relative to the total concentration of the aqueous medium and PTFE.

[0337] By including the above steps, an aqueous dispersion with a smaller average primary particle size and more excellent stability can be obtained. In addition, an aqueous dispersion with a smaller amount of un-precipitated polymer can be obtained. Furthermore, the aspect ratio of the primary particles can be further reduced.

[0338] In the step of continuously adding the above hydrocarbon surfactant, the addition amount of the hydrocarbon surfactant is preferably 0.01% to 10% by mass relative to 100% by mass of the aqueous medium. The more preferable lower limit is 0.05% by mass, the further preferable lower limit is 0.1% by mass, the more preferable upper limit is 5% by mass, and the further preferable upper limit is 1% by mass.

[0339] In the step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of the above hydrocarbon surfactant, the amount of the hydrocarbon surfactant is preferably relatively large, and is preferably 0.01% to 10% by mass relative to 100% by mass of the aqueous medium. The more preferable lower limit is 0.1% by mass, and the more preferable upper limit is 1% by mass.

[0340] The manufacturing method of the present invention preferably further includes the following steps: Before the start of polymerization or when the concentration of PTFE formed in the aqueous medium is 5.0% by mass or less, a modified monomer is added to the aqueous medium. By adding the modified monomer at the initial stage of polymerization, an aqueous dispersion with a small average primary particle size, a small aspect ratio of primary particles, and excellent stability can be obtained. That is, the above-mentioned modified monomer can be added before the start of polymerization, or added simultaneously with the start of polymerization, as long as it is added during the period of forming the nuclei of PTFE particles after the start of polymerization. For example, it is preferably added when the concentration of PTFE is 5.0% by mass or less.

[0341] Regarding the amount of the modified monomer added before the start of polymerization or when the concentration of PTFE formed in the aqueous medium is 5.0% by mass or less, relative to the obtained polytetrafluoroethylene, it is preferably 0.00001% by mass or more, preferably 0.0001% by mass or more, more preferably 0.0005% by mass, more preferably 0.001% by mass or more, and further preferably 0.003% by mass or more. The upper limit is not limited, for example, it is 1.0% by mass.

[0342] In the above polymerization step, the number of PTFE particles is preferably 6.0×10 12 pieces / mL or more. By increasing the number of PTFE particles (nuclei) in the initial stage of polymerization, an aqueous dispersion with a small average primary particle size, a small aspect ratio of primary particles, and excellent stability can be obtained. The number of the above PTFE particles is more preferably 7.0×10 12 pieces / mL or more, further preferably 8.0×10 12 pieces / mL or more, still more preferably 9.0×10 12 pieces / mL or more, and particularly preferably 1.0×10 13 pieces / mL or more. The upper limit is not particularly limited, for example, it is 7.0×10 14 pieces / mL.

[0343] In the above polymerization step, it is preferably to generate 0.6×10 13 pieces / ml or more of PTFE particles. By generating a large number of particles in the polymerization step, primary particles with a small average primary particle size and a small aspect ratio can be obtained, and an aqueous dispersion with excellent stability can be obtained. As the number of the generated PTFE particles, it is more preferably 0.7×10 13 pieces / mL or more, further preferably 0.8×10 13 pieces / mL or more, still more preferably 0.9×10 13 pieces / mL or more, and particularly preferably 1.0×10 13 pieces / mL or more. The upper limit is not particularly limited, for example, it is 7.0×10 14 pieces / mL.

[0344] Since PTFE particles are generated mainly in the first half of the polymerization process and it is difficult to generate them in the second half, the number of PTFE particles in the polymerization process is approximately the same as the number of particles generated in the first half of the polymerization. Therefore, the number of PTFE particles in the polymerization process can be predicted by measuring the number of primary particles in the finally obtained aqueous PTFE dispersion.

[0345] As the above-mentioned hydrocarbon-based surfactant, substances described in, for example, Japanese Patent Application Laid-Open No. 2013-542308, Japanese Patent Application Laid-Open No. 2013-542309, and Japanese Patent Application Laid-Open No. 2013-542310 can be used.

[0346] The above-mentioned hydrocarbon-based surfactant may be a surfactant having a hydrophilic part and a hydrophobic part on the same molecule. They can be cationic, nonionic, or anionic.

[0347] Cationic hydrocarbon-based surfactants generally have a positively charged hydrophilic part such as alkylated ammonium halides like alkylated ammonium bromide and a hydrophobic part such as long-chain fatty acids.

[0348] Anionic hydrocarbon-based surfactants generally have a hydrophilic part such as carboxylate, sulfonate, or sulfate and a hydrophobic part such as an alkyl as a long-chain hydrocarbon part.

[0349] Nonionic hydrocarbon-based 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 chains of ethylene ethers derived from the polymerization of ethylene oxide.

[0350] Examples of nonionic hydrocarbon-based surfactants

[0351] Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and their derivatives.

[0352] Specific examples of polyoxyethylene alkyl ethers: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, etc.

[0353] Specific examples of polyoxyethylene alkyl phenyl ethers: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, etc.

[0354] Specific examples of polyoxyethylene alkyl esters: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, etc.

[0355] Specific examples of sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.

[0356] Specific examples of polyoxyethylene sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, etc.

[0357] Specific examples of glycerol esters: glycerol monomyristate, glycerol monostearate, glycerol monooleate, etc.

[0358] Specific examples of the above derivatives: polyoxyethylene alkylamine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, etc.

[0359] The above ethers and esters may have an HLB value of 10 to 18.

[0360] As nonionic hydrocarbon surfactants, examples include 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, 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.

[0361] As anionic hydrocarbon surfactants, examples include Versatic (registered trademark) 10 of Resolution Performance Products, Avanel S series (S-70, S-74, etc.) manufactured by BASF, etc.

[0362] As the above hydrocarbon surfactants, examples also include those represented by R Z -L-M (wherein R Z is a linear or branched alkyl having 1 or more carbon atoms with or without substituents or a cyclic alkyl having 3 or more carbon atoms with or without substituents. When having 3 or more carbon atoms, 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, NR5Z 4. An imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5Z is H or an organic group, -ArSO3 - is an anionic surfactant represented by an arylsulfonate).

[0363] Specifically, examples include those represented by lauric acid, CH3-(CH2) n -L-M (where n is an integer from 6 to 17. L and M are the same as above).

[0364] It is also possible to use a mixture of substances where R Z is an alkyl group having 12 to 16 carbon atoms and L-M is sulfate or sodium dodecyl sulfate (SDS).

[0365] As other compounds having surface-active ability, examples also include those represented by R 6Z (-L-M)2 (where R 6Z is a linear or branched alkylene group with or without substituents and having 1 or more carbon atoms, or a cyclic alkylene group with or without substituents and having 3 or more carbon atoms. When having 3 or more carbon atoms, 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 5Z 4. An imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5Z is H or an organic group, -ArSO3 - is an anionic surfactant represented by an arylsulfonate).

[0366] As the above hydrocarbon-based surfactant, examples also include those represented by R 7Z (-L-M)3 (where R 7Z is a linear or branched alkylene group with or without substituents and having 1 or more carbon atoms, or a cyclic alkylene group with or without substituents and having 3 or more carbon atoms. When having 3 or more carbon atoms, 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 5Z4. Imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, R 5Z is H or an organic group. -ArSO3 - is an anionic surfactant represented by an arylsulfonate).

[0367] The above-mentioned R 5z is preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms.

[0368] In this specification, unless otherwise specified, "substituent" refers to a group that can substitute. Examples of such "substituents" include: aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, acyloxy groups, acylamino groups, aliphatic oxy groups, aromatic oxy groups, heterocyclic oxy groups, aliphatic oxycarbonyl groups, aromatic oxycarbonyl groups, heterocyclic oxycarbonyl groups, carbamoyl groups, aliphatic sulfonyl groups, aromatic sulfonyl groups, heterocyclic sulfonyl groups, aliphatic sulfonyloxy groups, aromatic sulfonyloxy groups, heterocyclic sulfonyloxy groups, sulfamoyl groups, aliphatic sulfonamide groups, aromatic sulfonamide groups, heterocyclic sulfonamide groups, amino groups, aliphatic amino groups, aromatic amino groups, heterocyclic amino groups, aliphatic oxycarbonylamino groups, aromatic oxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxyl groups, cyano groups, sulfo groups, carboxyl groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, di-aliphatic oxyphosphinyl groups or di-aromatic oxyphosphinyl groups.

[0369] As the above-mentioned hydrocarbon-based surfactant, a silicone hydrocarbon-based surfactant can also be cited. As the silicone hydrocarbon-based 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-based 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.

[0370] In the case where the carbon atoms of the hydrocarbon group can be substituted by halogens such as fluorine, these silicone hydrocarbon-based surfactants can also be regarded as hydrocarbon-based surfactants in the sense that they are completely substituted by hydrogen atoms, that is, the monovalent substituents on the carbon atoms of the hydrocarbon group are hydrogen.

[0371] The hydrophilic moiety of the siloxane hydrocarbon surfactant may include one or more polar moieties 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 moiety may also include an ionically functionalized siloxane graft.

[0372] Examples of such siloxane hydrocarbon surfactants include, for example, polydimethylsiloxane-grafted-(meth)acrylate, polydimethylsiloxane-grafted-polyacrylate salt, and polydimethylsiloxane-grafted quaternary amine.

[0373] The polar moiety of the hydrophilic moiety of the siloxane hydrocarbon surfactant may include: 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) may vary in the mixed polyethylene oxide / propylene oxide polyether.

[0374] The hydrophilic moiety of the siloxane hydrocarbon surfactant may also include a combination of an ionic moiety and a nonionic moiety. Examples of such moieties include, for example, polyethers or polyols that are ionically end-functionalized or randomly functionalized. Preferred in the practice of the present invention are siloxanes having a nonionic moiety, i.e., nonionic siloxane surfactants.

[0375] The configuration of the hydrophobic and hydrophilic moieties of the structure of the siloxane hydrocarbon surfactant may take the form of a diblock polymer (AB), a triblock polymer (ABA) (here, "B" represents the siloxane moiety of the molecule), or a multiblock polymer. Alternatively, the siloxane surfactant may include a graft polymer.

[0376] The siloxane hydrocarbon surfactant is also disclosed in U.S. Patent No. 6,841,616.

[0377] Examples of anionic hydrocarbon surfactants based on a siloxane matrix 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.

[0378] As an anionic hydrocarbon surfactant, sulfosuccinate surfactants such as Lankropol (registered trademark) K8300 of Akzo Nobel Surface Chemistry LLC can also be cited.

[0379] As sulfosuccinate surfactants, sodium diisodecyl sulfosuccinate, (Emulsogen (registered trademark) SB10 of Clariant), sodium bis(isotridecyl) sulfosuccinate (Polirol (registered trademark) TR / LNA of Cesapinia Chemicals), etc. can be cited.

[0380] As the above-mentioned hydrocarbon surfactants, PolyFox (registered trademark) surfactants (PolyFox TM PF-156A, PolyFox TM PF-136A, etc.) of Omnova Solutions, Inc. can also be cited.

[0381] As the above-mentioned hydrocarbon surfactants, anionic hydrocarbon surfactants are preferred. As anionic hydrocarbon surfactants, the above-mentioned substances can be used, and for example, the following anionic hydrocarbon surfactants can be suitably used.

[0382] As the above-mentioned anionic hydrocarbon surfactants, for example, the following formula (α) can be cited:

[0383] R 100 -COOM (α)

[0384] (In the formula, R 100 is a monovalent organic group containing one or more carbon atoms. M is H, a metal atom, NR 101 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 101 is H or an organic group, which may be the same or different) the compound (α) shown. As the organic group of R 101 , an alkyl group is preferred. As R 101 , H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms.

[0385] From the aspect of surface activity ability, the number of carbon atoms of R 100 is preferably 2 or more, more preferably 3 or more. In addition, from the aspect of water solubility, the number of carbon atoms of R 100 is preferably 29 or less, more preferably 23 or less.

[0386] As the metal atom of M described above, alkali metals (Group 1), alkaline earth metals (Group 2), etc. can be mentioned, and Na, K or Li is preferred. As M, H, a metal atom or NR 101 4 is more preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 101 4 is further preferred, and H, Na, K, Li or NH4 is even more preferred, and Na, K or NH4 is still more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0387] As the above compound (α), those represented by R 102 -COOM (wherein R 102 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 also form a ring. M is the same as above) can also be mentioned. 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 mentioned.

[0388] From the aspect of emulsion stability, the above compound (α) may not contain a carbonyl group (excluding the carbonyl group in the carboxyl group).

[0389] As the hydrocarbon-containing surfactant that does not contain a carbonyl group described above, for example, the following formula (A) is preferably exemplified:

[0390] R 103 -COO-M(A)

[0391] (wherein R 103 is an alkyl, alkenyl, alkylene or alkenylene containing 6 to 17 carbon atoms, and they may contain an ether bond. M is H, a metal atom, NR 101 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents. R 101 are the same or different and are H or an organic group) compounds.

[0392] In the above formula (A), R 103 is preferably an alkyl or alkenyl (they may contain an ether group). The alkyl or alkenyl in the above R 103 can be linear or branched. The number of carbon atoms of the above R 103 is not limited and is, for example, 2 to 29.

[0393] When the above alkyl is linear, R 103The number of carbon atoms is preferably 3 to 29, more preferably 5 to 23. When the above alkyl group is branched, R 103 The number of carbon atoms is preferably 5 to 35, more preferably 11 to 23.

[0394] When the above alkenyl group is linear, R 103 The number of carbon atoms is preferably 2 to 29, more preferably 9 to 23. When the above alkenyl group is branched, R 103 The number of carbon atoms is preferably 4 to 29, more preferably 9 to 23.

[0395] Examples of the above alkyl and alkenyl groups include methyl, ethyl, isobutyl, tert-butyl, vinyl, and the like.

[0396] Examples of the above compound (α) (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, isolenic 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, isolenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-elaeostearic acid, β-elaeostearic acid, eicosatrienoic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, docosatetraenoic acid, eicosapentaenoic acid, docosapentaenoic acid, sardine acid, clupanodonic acid, and salts thereof.

[0397] Particularly preferred is at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof.

[0398] Examples of the above salt include salts in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 101 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, and there is no particular limitation.

[0399] As the above surfactant (α) (carboxylic acid type hydrocarbon surfactant), since particles with a small average primary particle diameter can be obtained by polymerization and a large number of particles are generated during polymerization, polytetrafluoroethylene can be efficiently manufactured. Therefore, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and their salts is preferably selected, lauric acid and its salts are more preferably selected, salts of lauric acid are particularly preferably selected, and sodium laurate and ammonium laurate are most preferably selected.

[0400] As the above hydrocarbon surfactant, the following general formula (1) is preferably exemplified:

[0401] [Chemical formula 11]

[0402]

[0403] (In the formula, R 1 ~R 5 represents H or a monovalent substituent. Among them, at least one of R 1 and R 3 represents a group represented by the general formula: -Y-R 6 shown, and at least one of R 2 and R 5 represents a group represented by the general formula: -X-A or a group represented by the general formula: -Y-R 6 shown.

[0404] In addition, X is the same or different each time it appears, and is a divalent linking group or a bonding bond;

[0405] A is the same or different each time it appears, and represents -COOM, -SO3M or -OSO3M (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);

[0406] Y is the same or different each time it appears, and represents a divalent linking group or a bonding bond selected from the group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 -, and -NR 8 CO-, and R 8 is H or an organic group;

[0407] R 6 is the same or different each time it appears, and represents an alkyl group having 2 or more carbon atoms that may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon-carbon atoms.

[0408] R 1 ~R 5Any two of them can be bonded to each other to form a ring) the surfactant shown below (hereinafter also referred to as surfactant (1)).

[0409] The surfactant (1) will be described.

[0410] In the formula, R 1 ~R 5 represents H or a monovalent substituent, wherein at least one of R 1 and R 3 represents a group represented by the general formula: -Y-R 6 shown, and at least one of R 2 and R 5 represents a group represented by the general formula: -X-A or a group represented by the general formula: -Y-R 6 shown. Any two of R 1 ~R 5 can be bonded to each other to form a ring.

[0411] As the above-mentioned substituent that the above-mentioned alkyl group of R 1 can have, it is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

[0412] As the above-mentioned alkyl group of R 1 it preferably does not contain a carbonyl group.

[0413] In the above-mentioned alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0414] The above-mentioned alkyl group preferably does not have any substituents.

[0415] As R 1 , it is preferably a linear or branched alkyl group having 1 to 10 carbon atoms with or without substituents or a cyclic alkyl group having 3 to 10 carbon atoms with or without substituents, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group, further preferably a linear or branched alkyl group having 1 to 10 carbon atoms that does not have substituents, and still further preferably a linear or branched alkyl group having 1 to 3 carbon atoms that does not have substituents, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0416] As the monovalent substituent, it is preferably a group represented by the general formula: -Y-R 6 shown, a group represented by the general formula: -X-A, -H, C with or without substituents1-20 alkyl, -NH2, -NHR 9 (R 9 is an organic group), -OH, -COOR 9 (R 9 is an organic group) or -OR 9 (R 9 is an organic group). The alkyl group preferably has 1 to 10 carbon atoms.

[0417] As R 9 , preferably an alkyl group of C 1-10 or an alkylcarbonyl group of C 1-10 , more preferably an alkyl group of C 1-4 or an alkylcarbonyl group of C 1-4 .

[0418] In the formula, X is the same or different each time it appears and represents a divalent linking group or a bond.

[0419] R 6 When not containing any of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X is preferably a divalent linking group containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0420] As X, preferably a divalent linking group containing at least one bond selected from the group consisting of -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -O-S(=O)2-, -CONR 8 -, and -NR 8 CO-, an alkylene group of C 1-10 , or a bond. R 8 represents H or an organic group.

[0421] As the organic group in R 8 , preferably an alkyl group. As R 8 , 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 organic group of C 1-4 , and even more preferably H.

[0422] In the formula, A is the same or different each time it appears and represents -COOM, -SO3M, or -OSO3M (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. The four R 7 can be the same or different). In general formula (1), A being -COOM is one of the preferred forms.

[0423] As R 7 in the organic group, an alkyl group is preferred. As R 7 , H or C 1-10 is preferred as the organic group, and more preferably H or C 1-4 is preferred as the organic group, and still more preferably H or C 1-4 is preferred as the alkyl group.

[0424] As the above metal atom, an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be mentioned, and Na, K or Li is preferred.

[0425] As M, H, a metal atom or NR 7 4 is preferred, and 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.

[0426] In the formula, Y is the same or different each time it appears, and represents a divalent linking group or a bonding bond selected from the group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 CO-, and R 8 represents H or an organic group.

[0427] As Y, a divalent linking group selected from the group consisting of a bonding bond, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 CO- is preferred, and a divalent linking group selected from the group consisting of a bonding bond, -COO- and -OCO- is more preferred.

[0428] As the organic group in R 8 , an alkyl group is preferred. As R 8 , H or C 1-10 is preferred as the organic group, and more preferably H or C 1-4 is preferred as the organic group, and still more preferably H or C 1-4 is preferred as the alkyl group, and still further preferably H.

[0429] In the formula, R 6 is the same or different each time it appears, and represents an alkyl group having 2 or more carbon atoms which may or may not contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms. The number of carbon atoms of the above R 6 organic group is preferably 2 to 20, and more preferably 2 to 10.

[0430] R 6The alkyl group can contain one or more than two groups selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon-carbon atoms, but these groups are not contained at the end of the alkyl group. The above R 6 In the alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0431] As R 6 , preferably

[0432] General formula: -R 10 -CO-R 11 The group shown,

[0433] General formula: -R 10 -COO-R 11 The group shown,

[0434] General formula: -R 11 The group shown,

[0435] General formula: -R 10 -NR 8 CO-R 11 The group shown, or

[0436] General formula: -R 10 -CONR 8 -R 11 The group shown

[0437] (In the formula, R 8 represents H or an organic group. R 10 is an alkylene group, and R 11 is an alkyl group with or without substituents).

[0438] As R 6 , more preferably the group represented by the general formula: -R 10 -CO-R 11 shown.

[0439] As the organic group in R 8 , an alkyl group is preferred. As R 8 , preferably H or C 1-10 organic group, more preferably H or C 1-4 organic group, further preferably H or C 1-4 alkyl group, and even more preferably H.

[0440] R 10The number of carbon atoms of the alkylene group is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. In addition, R 10 The number of carbon atoms of the alkylene group is preferably 1 to 20, more preferably 1 to 10, and further preferably 3 to 10.

[0441] R 11 The number of carbon atoms of the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10, still more preferably 1 to 8, particularly more preferably 1 to 6, particularly further preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. In addition, the above-mentioned R 11 The alkyl group is preferably composed only of primary carbon, secondary carbon, and tertiary carbon, and particularly preferably composed only of primary carbon and secondary carbon. That is, as R 11 , methyl, ethyl, n-propyl, and isopropyl are preferred, and particularly most preferred is methyl.

[0442] In the general formula (1), at least one of R 2 and R 5 is a group represented by the general formula: -X-A, and it is also one of the preferred embodiments that A is -COOM.

[0443] As the surfactant (1), the compound represented by the general formula (1-1), the compound represented by the general formula (1-2), or the compound represented by the general formula (1-3) is preferred, and the compound represented by the general formula (1-1) or the compound represented by the general formula (1-2) is more preferred.

[0444] General formula (1-1):

[0445] [Chemical formula 12]

[0446]

[0447] (In the formula, R 3 ~R 6 , X, A, and Y are as described above.)

[0448] General formula (1-2):

[0449] [Chemical formula 13]

[0450]

[0451] (In the formula, R 4 ~R 6 , X, A, and Y are as described above.) General formula (1-3):

[0452] [Chemical formula 14]

[0453]

[0454] (wherein, R 2 , R 4 ~R 6 , X, A and Y are as described above.) As the group represented by the general formula: -X-A, preferably -COOM,

[0455] -R 12 COOM,

[0456] -SO3M,

[0457] -OSO3M, -R 12 SO3M,

[0458] -R 12 OSO3M,

[0459] -OCO-R 12 -COOM,

[0460] -OCO-R 12 -SO3M,

[0461] -OCO-R 12 -OSO3M

[0462] -COO-R 12 -COOM,

[0463] -COO-R 12 -SO3M,

[0464] -COO-R 12 -OSO3M,

[0465] -CONR 8 -R 12 -COOM,

[0466] -CONR 8 -R 12 -SO3M,

[0467] -CONR 8 -R 12 -OSO3M,

[0468] -NR 8 CO-R 12 -COOM,

[0469] -NR 8 CO-R 12 -SO3M,

[0470] -NR 8 CO-R 12 -OSO3M,

[0471] -OS(=O)2-R 12 -COOM,

[0472] -OS(=O)2-R 12 -SO3M, or

[0473] -OS(=O)2-R 12 -OSO3M

[0474] (wherein R 8 and M are as described above. R 12 is an alkylene of C 1-10 ).

[0475] Among the alkylene groups of the above R 12 , up to 75%, up to 50%, or up to 25% of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, but a non-halogenated alkylene group free of halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0476] As the group represented by the general formula: -Y-R 6 , preferably

[0477] the group represented by the general formula: -R 10 -CO-R 11 ,

[0478] the group represented by the general formula: -OCO-R 10 -CO-R 11 ,

[0479] the group represented by the general formula: -COO-R 10 -CO-R 11 ,

[0480] the group represented by the general formula: -OCO-R 10 -COO-R 11 ,

[0481] the group represented by the general formula: -COO-R 11 ,

[0482] the group represented by the general formula: -NR 8 CO-R 10 -CO-R 11 , or

[0483] the group represented by the general formula: -CONR 8 -R 10 -NR 8 CO-R 11 ,

[0484] (wherein R 8 , R 10 and R11 As described above.)

[0485] In the formula, as R 4 and R 5 , independently, are preferably H or an alkyl group of C 1-4 .

[0486] Among the above-mentioned R 4 and R 5 alkyl groups, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but are preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0487] As R 3 in the general formula (1-1), it is preferably H or an alkyl group of C 1-20 with or without substituents, more preferably H or an alkyl group of C 1-20 without substituents, and still more preferably H.

[0488] Among the above-mentioned R 3 alkyl groups, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but are preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0489] As R 2 in the general formula (1-3), it is preferably H, OH or an alkyl group of C 1-20 with or without substituents, more preferably H, OH or an alkyl group of C 1-20 without substituents, and still more preferably H or OH.

[0490] Among the above-mentioned R 2 alkyl groups, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but are preferably non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0491] As the above-mentioned hydrocarbon-based surfactant, the following formula (1-0A) can also be cited:

[0492] [Chemical formula 15]

[0493]

[0494] (In the formula, R 1A to R 5A are H, a monovalent hydrocarbon group that may contain an ester group between carbon-carbon atoms, or a group represented by the general formula: -X A -A. However, R 2A and R5A at least one of which represents a general formula: -X A -A group represented by

[0495] X A is the same or different each time it appears, and is a divalent hydrocarbon group or a bonding bond;

[0496] A is the same or different each time it appears, and is -COOM (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);

[0497] R 1A ~R 5A any two of which can be bonded to each other to form a ring) a surfactant (1-0A) and the like.

[0498] In the general formula (1-0A), among R 1A ~R 5A the number of carbon atoms of the monovalent hydrocarbon group that may contain an ester group between carbon-carbon atoms is preferably 1 to 50, more preferably 5 to 20. R 1A ~R 5A any two of which can be bonded to each other to form a ring. As the monovalent hydrocarbon group that may contain an ester group between carbon-carbon atoms, an alkyl group is preferred.

[0499] In the formula, among X A the number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 50, more preferably 5 to 20. As the above divalent hydrocarbon group, an alkylene group, an alkane diyl group, etc. can be cited, and an alkylene group is preferred.

[0500] In the general formula (1-0A), R 2A and R 5A any one of which is preferably the group represented by the general formula: -X A -A, more preferably R 2A is the group represented by the general formula: -X A -A.

[0501] In the general formula (1-0A), as a preferred mode, R 2A is the group represented by the general formula: -X A -A, R 1A , R 3A , R 4A and R 5A are H. In this case, X A is preferably a bonding bond or an alkylene group having 1 to 5 carbon atoms.

[0502] In the general formula (1-0A), as a preferred embodiment, it is also the following embodiment: R 2A is a group represented by the general formula: -X A -A, R 1A and R 3A is a group represented by -Y A -R 6 where Y A is the same or different each time it appears, and is -COO-, -OCO-, or a bonding bond, and R 6 is the same or different each time it appears, and is an alkyl group having 2 or more carbon atoms. In this case, R 4A and R 5A are preferably H.

[0503] As the hydrocarbon surfactant represented by the general formula (1-0A), for example, glutaric acid or its salt, adipic acid or its salt, pimelic acid or its salt, suberic acid or its salt, azelaic acid or its salt, sebacic acid or its salt, etc. can be cited.

[0504] In addition, the aliphatic carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) can be a double-chain di-hydrophilic group type synthetic surfactant. For example, as a Gemini type surfactant, Gemini Surf (Chukyo Yushi Co., Ltd.), Gemsurfα142 (lauryl group with 12 carbon atoms), Gemsurfα102 (10 carbon atoms), Gemsurfα182 (14 carbon atoms), etc. can be cited.

[0505] As the above hydrocarbon surfactant, a hydrocarbon surfactant having 1 or more carbonyl groups (excluding the carbonyl group in the carboxyl group) can also be cited.

[0506] In addition, a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having 1 or more carbonyl groups (excluding the carbonyl group in the carboxyl group) to a radical treatment or an oxidation treatment can also be used.

[0507] The above radical treatment is only required to be a treatment that generates radicals in a hydrocarbon surfactant having 1 or more carbonyl groups (excluding the carbonyl group in the carboxyl group). For example, it is the following treatment: Add deionized water and a hydrocarbon surfactant to a reactor, seal the reactor, displace the inside of the system with nitrogen, heat and pressurize the reactor, then add a polymerization initiator, stir for a certain time, and then depressurize the reactor until it reaches atmospheric pressure and cool it. The above oxidation treatment is a treatment of adding an oxidizing agent to a hydrocarbon surfactant having 1 or more carbonyl groups (excluding the carbonyl group in the carboxyl group). As the oxidizing agent, for example, oxygen, ozone, hydrogen peroxide, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide, etc. can be cited.

[0508] As the above hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), the following formula is preferred: R X -X X (In the formula, R X is a non-fluorinated organic group having 1 to 2000 carbon atoms and one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), and X X is -OSO3X X1 , -COOX X1 or -SO3X X1 (X X1 is H, a metal atom, NR X1 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R X1 is H or an organic group, which may be the same or different)). The surfactant represented by the formula. The number of carbon atoms of R X is preferably 500 or less, more preferably 100 or less, further preferably 50 or less, and still more preferably 30 or less. As the organic group of R X1 , an alkyl group is preferred. As R X1 , H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms.

[0509] As the above hydrocarbon surfactant, it is more preferably selected from the following formula (a):

[0510] [Chemical formula 16]

[0511]

[0512] (In the formula, R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. The hydrogen atom bonded to the carbon atom may be replaced by a hydroxyl group or a monovalent organic group containing an ester bond. When the number of carbon atoms is 2 or more, a carbonyl group may be included. When the number of carbon atoms is 3 or more, a monovalent or divalent heterocycle may be included or a ring may be formed. R 2a and R 3a are independently a single bond or a divalent linking group. R 1a , R 2a and R 3a The total number of carbon atoms is 6 or more. X a is H, a metal atom, NR 4a 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 4a is H or an organic group, which may be the same or different. R 1a , R2a and R 3a Any two of them can be bonded to each other to form a ring) The surfactant (a) shown below, the following formula (b):

[0513] [Chemical formula 17]

[0514]

[0515] (In the formula, R 1b 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. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. R 2b and R 4b are independently H or a substituent. R 3b is an alkylene group having 1 to 10 carbon atoms with or without substituents. n is an integer of 1 or more. p and q are independently integers of 0 or more. X b is H, a metal atom, NR 5b 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5b is H or an organic group, and may be the same or different. R 1b , R 2b , R 3b and R 4b Any two of them can be bonded to each other to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-*, or -CO- (excluding the carbonyl groups included in -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without substituents, R 6b is H or an alkyl group having 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to -OSO3X b in the formula) The surfactant (b) shown below, the following formula (c):

[0516] [Chemical formula 18]

[0517]

[0518] (In the formula, R 1cis a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, and the hydrogen atom bonded to the carbon atom may be replaced by a hydroxyl group or a monovalent organic group containing an ester bond. When the number of carbon atoms is 2 or more, a carbonyl group may be included. When the number of carbon atoms is 3 or more, a monovalent or divalent heterocycle may be included or a ring may be formed. R 2c and R 3c are independently a single bond or a divalent linking group. R 1c 、R 2c and R 3c have a total of 5 or more carbon atoms. A c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 4c is H or an organic group, and may be the same or different). R 1c 、R 2c and R 3c Any two of them may be bonded to each other to form a ring), a surfactant (c) represented by the following formula (d):

[0519] [Chemical formula 19]

[0520]

[0521] (In the formula, R 1d 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. When the number of carbon atoms is 3 or more, a monovalent or divalent heterocycle may be included or a ring may be formed. R 2d and R 4d are independently H or a substituent. R 3d is an alkylene group having 1 to 10 carbon atoms with or without substituents. n is an integer of 1 or more. p and q are independently integers of 0 or more. A d is -SO3X d or -COOX d (X d is H, a metal atom, NR 5d 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 5d is H or an organic group, and may be the same or different). R 1d 、R 2d 、R 3d and R 4dAny two of them can be bonded to each other to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding the carbonyl groups contained in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without substituents, R 6d is H or an alkyl group having 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to A in the formula d At least one selected from the group consisting of the surfactant (d) shown).

[0522] The surfactant (a) will be described.

[0523] In formula (a), R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0524] When the number of carbon atoms of the above alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be included between two carbon atoms. In addition, when the number of carbon atoms of the above alkyl group is 2 or more, the above carbonyl group may also be included at the end of the above alkyl group. That is, acyl groups such as the acetyl group represented by CH3-C(=O)- are also included in the above alkyl group.

[0525] In addition, when the number of carbon atoms of the above alkyl group is 3 or more, a monovalent or divalent heterocycle may be included and a ring may also be formed. As the above heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred. For example, a furan ring can be cited. In R 1a For the divalent heterocycle, it can be inserted between two carbon atoms, the divalent heterocycle can also be located at the end and bonded to -C(=O)-, and the monovalent heterocycle can be located at the end of the above alkyl group.

[0526] It should be noted that in this specification, the "number of carbon atoms" of the above alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above heterocycle. For example, the number of carbon atoms of the group represented by CH3-C(=O)-CH2- is 3, the number of carbon atoms of the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- is 7, and the number of carbon atoms of the group represented by CH3-C(=O)- is 2.

[0527] In the above alkyl group, the hydrogen atom bonded to the carbon atom can be replaced by a functional group. For example, it can be replaced by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not replaced by any functional group.

[0528] As the monovalent organic group containing an ester bond described above, a group represented by the formula: -O-C(=O)-R 101a (In the formula, R 101a is an alkyl group) can be mentioned.

[0529] In the above alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, 25% or less may be substituted by halogen atoms, but a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0530] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group.

[0531] R 2a and R 3a are preferably independently a single bond, or a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0532] The above-mentioned alkylene group constituting R 2a and R 3a preferably does not contain a carbonyl group.

[0533] In the above alkylene group, the hydrogen atoms bonded to carbon atoms may be substituted by a functional group, for example, may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0534] As the monovalent organic group containing an ester bond described above, a group represented by the formula: -O-C(=O)-R 102a (In the formula, R 102a is an alkyl group) can be mentioned.

[0535] In the above alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, 25% or less may be substituted by halogen atoms, but a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0536] R 1a 、R 2a and R 3a The total number of carbon atoms of and is 6 or more. As the total number of carbon atoms, 8 or more is preferred, more preferably 9 or more, still more preferably 10 or more, and 20 or less is preferred, more preferably 18 or less, still more preferably 15 or less.

[0537] R 1a 、R 2a and R 3a Any two of them may be bonded to each other to form a ring.

[0538] In formula (a), X a is H, a metal atom, NR 4a 4, imidazolium with or without substituents, pyridinium with or without substituents, or phosphonium with or without substituents, and R 4a is H or an organic group. The four Rs 4a can be the same or different. As the organic group in R 4a , an alkyl group is preferred. As R 4a , H or an organic group having 1 to 10 carbon atoms is preferred, an organic group having 1 to 4 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is further preferred. As the above metal atom, monovalent and divalent metal atoms can be mentioned, such as alkali metals (Group 1), alkaline earth metals (Group 2), etc., and Na, K or Li is preferred.

[0539] As X a , H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4a 4 is preferred. For the reason of being easily soluble in water, H, Na, K, Li or NH4 is more preferred. For the reason of being more easily soluble in water, Na, K or NH4 is further preferred, Na or NH4 is particularly preferred, and NH4 is most preferred for the reason of being easily removed. When X a is NH4, the above surfactant has excellent solubility in an aqueous medium and is not likely to leave a metal component in PTFE or the final product.

[0540] As R 1a , a linear or branched alkyl group having 1 to 8 carbon atoms not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms containing a monovalent or divalent heterocycle is preferred.

[0541] In addition, as R 1a , the following formula is more preferred:

[0542] [Chemical formula 20]

[0543]

[0544] (In the formula, n 11a is an integer from 0 to 10, R 11a is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R 12a is an alkylene group having 0 to 3 carbon atoms. When n 11a is an integer from 2 to 10, R 12agroups as described above which may be the same or different, respectively).

[0545] As n 11a , preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and still more preferably an integer of 1 to 3.

[0546] As R 11a the above-mentioned alkyl group preferably does not contain a carbonyl group.

[0547] As R 11a in the above-mentioned alkyl group as R, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, it may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0548] As the above-mentioned monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 103a (wherein, R 103a is an alkyl group) can be cited.

[0549] As R 11a in the above-mentioned alkyl group as R, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, 25% or less may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0550] R 12a is an alkylene group having 0 to 3 carbon atoms. The above-mentioned number of carbon atoms is preferably 1 to 3.

[0551] As R 12a the above-mentioned alkylene group may be linear or branched.

[0552] As R 12a the above-mentioned alkylene group preferably does not contain a carbonyl group. As R 12a , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0553] As R 12a in the above-mentioned alkylene group as R, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, it may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0554] As the above-mentioned monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 104a (wherein, R 104a is an alkyl group) can be cited.

[0555] As R 12aIn the above-mentioned alkylene group, 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, but a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0556] As R 2a and R 3a , it is preferably an alkylene group having 1 or more carbon atoms that does not contain a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms that does not contain a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0557] As the surfactant (a), the following surfactants can be exemplified. In each formula, X a As described above.

[0558] [Chemical formula 21]

[0559]

[0560] [Chemical formula 22]

[0561]

[0562] [Chemical formula 23]

[0563]

[0564] [Chemical formula 24]

[0565]

[0566] [Chemical formula 25]

[0567]

[0568] [Chemical formula 26]

[0569]

[0570] [Chemical formula 27]

[0571]

[0572] [Chemical formula 28]

[0573]

[0574] The surfactant (a) is a new compound and can be produced, for example, by the production methods exemplified below.

[0575] The surfactant (a) can be produced by a production method including the following steps (11a), (12a), (13a), and (14a), where

[0576] Step (11a) involves reacting a compound (10a) represented by the formula:

[0577] [Chemical formula 29]

[0578]

[0579] (wherein R 3a As described above, E a is a leaving group), lithium, and a chlorosilane compound represented by the formula: R 201a 3Si-Cl (wherein R 201a is independently an alkyl or aryl group) to obtain a compound (11a) represented by the formula:

[0580] [Chemical formula 30]

[0581]

[0582] (wherein R 3a , R 201a and E a are as described above),

[0583] Step (11b) involves reacting the compound (11a) with an olefin represented by the formula:

[0584] [Chemical formula 31]

[0585]

[0586] (wherein R 1a is as described above, and R 21a is a single bond or a divalent linking group) to obtain a compound (12a) represented by the formula:

[0587] [Chemical formula 32]

[0588]

[0589] (wherein R 1a , R 21a , R 3a and E a are as described above),

[0590] Step (13a) involves removing the leaving group present in the compound (12a) to obtain a compound represented by the formula:

[0591] [Chemical formula 33]

[0592]

[0593] (wherein R 1a , R 21a and R 3aThe process of the compound (13a) as described above

[0594] In step (14a), the compound (13a) is reacted with chlorosulfonic acid of the formula:

[0595] [Chemical formula 34]

[0596]

[0597] (wherein X a as described above) to obtain a compound of the formula:

[0598] [Chemical formula 35]

[0599]

[0600] (wherein R 1a , R 21a , R 3a and X a as described above) of the compound (14a).

[0601] When R 1a contains a furan ring, for example, the furan ring can be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[0602] In step (11a), it is preferred to react lithium with the above-mentioned chlorosilane compound in advance to obtain a lithium silyloxy compound, and then react the lithium silyloxy compound with the compound (10a) to obtain the compound (11a).

[0603] E a represents a leaving group. Examples of the leaving group include tert-butyldimethylsilyl (TBS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), benzyl (Bn), etc.

[0604] As R 21a , a single bond or a linear or branched alkylene group having 1 or more carbon atoms is preferred.

[0605] Examples of the chlorosilane compound include

[0606] [Chemical formula 36]

[0607]

[0608] All reactions in step (11a) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred. As the above ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether, crown ethers (15-crown-5, 18-crown-6), etc. can be mentioned. Among them, tetrahydrofuran and diethyl ether are preferred.

[0609] As the temperature of the reaction between lithium and the above chlorosilane compound in step (11a), 10°C to 40°C is preferred, and 20°C to 30°C is more preferred.

[0610] As the temperature of the reaction between the above lithium silyloxide compound and compound (10a) in step (11a), -100°C to 0°C is preferred, and -80°C to -50°C is more preferred.

[0611] As the pressure of the reaction between lithium and the above chlorosilane compound in step (11a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0612] As the pressure of the reaction between the above lithium silyloxide compound and compound (10a) in step (11a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0613] As the reaction time between lithium and the above chlorosilane compound in step (11a), 0.1 hour to 72 hours is preferred, and 6 hours to 10 hours is more preferred.

[0614] As the reaction time between the above lithium silyloxide compound and compound (10a) in step (11a), 0.1 hour to 72 hours is preferred, and 1 hour to 2 hours is more preferred.

[0615] In step (12a), as the reaction ratio of compound (11a) and the above olefin, considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (11a), the above olefin is preferably 1 mole to 2 moles, and more preferably 1 mole to 1.1 moles.

[0616] The reaction in step (12a) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0617] As the above thiazolium salt, 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide, 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride, etc. can be mentioned.

[0618] As the above-mentioned base, 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, etc. can be cited.

[0619] As the above-mentioned solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an alcohol or an ether is further preferred.

[0620] As the above-mentioned alcohol, methanol, ethanol, 1-propanol, isopropanol, etc. can be cited.

[0621] As the above-mentioned ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. can be cited, and among them, tetrahydrofuran and diethyl ether are preferred.

[0622] As the temperature of the reaction in step (12a), 40°C to 60°C is preferred, and 50°C to 55°C is more preferred.

[0623] As the pressure of the reaction in step (12a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0624] As the reaction time in step (12a), 0.1 hour to 72 hours is preferred, and 6 hours to 10 hours is more preferred.

[0625] The elimination reaction of the leaving group in step (13a) can be carried out by using fluoride ions or an acid. As the method for eliminating the leaving group, for example, the following methods can be cited: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF; a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0626] The elimination reaction of the leaving group in step (13a) can be carried out in a solvent. As the above-mentioned solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0627] As the above-mentioned ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc. can be cited, and among them, tetrahydrofuran and diethyl ether are preferred.

[0628] As the temperature of the reaction in step (13a), 0 to 40°C is preferred, and 0 to 20°C is more preferred.

[0629] As the pressure of the reaction in step (13a), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[0630] As the reaction time in step (13a), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 8 hours.

[0631] In step (14a), as the reaction ratio of compound (13a) to the above-mentioned chlorosulfonic acid, in consideration of improving the yield and reducing waste, relative to 1 mole of compound (13a), the above-mentioned chlorosulfonic acid is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[0632] The reaction in step (14a) is preferably carried out in the presence of a base. Examples of the above-mentioned base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc., and amines are preferred.

[0633] Examples of the above-mentioned amine in step (14a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethyl-1,8-naphthalenediamine, etc., heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, etc., and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. Among them, triethylamine and pyridine are preferred.

[0634] Regarding the dosage of the above-mentioned base in step (14a), in consideration of improving the yield and reducing waste, relative to 1 mole of compound (13a), it is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[0635] The reaction in step (14a) can be carried out in a polar solvent. As the above-mentioned solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0636] Examples of the above-mentioned ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), crown ethers (15-crown-5, 18-crown-6), etc., and diethyl ether is preferred among them.

[0637] As the reaction temperature in step (14a), it is preferably 0 to 40 °C, more preferably 0 to 20 °C.

[0638] As the reaction pressure in step (14a), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[0639] As the reaction time in step (14a), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 12 hours.

[0640] When the reaction in step (14a) is carried out in a solvent, after the above reaction is terminated, a solution containing compound (14a) is obtained. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off, whereby high-purity compound (14a) can be recovered. When compound (14a) has a group represented by -OSO3H (i.e., when X is H), by using an aqueous alkali solution such as aqueous sodium bicarbonate solution or ammonia water instead of water, -OSO3H can also be converted into a sulfate group.

[0641] After each step is terminated, the solvent can be distilled off or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[0642] Surfactant (a) can also be produced by a production method including the following steps (21a), step (22a), and step (23a), wherein

[0643] Step (21a) is to make the formula:

[0644] [Chemical formula 37]

[0645]

[0646] (In the formula, R 3a As described above, R 22a is a monovalent organic group, and E a is a leaving group) of the ketone react with the formula:

[0647] [Chemical formula 38]

[0648]

[0649] (In the formula, R 1a As described above, R 23a is a monovalent organic group) of the carboxylic acid ester to obtain the formula:

[0650] [Chemical formula 39]

[0651]

[0652] (In the formula, R 1a , R 3a and E a As described above, R 24a is a single bond or a divalent linking group) of the compound (21a) of the step,

[0653] Step (22a) is to remove the leaving group possessed by compound (21a) to obtain the formula:

[0654] [Chemical formula 40]

[0655]

[0656] (In the formula, R 1a , R 24a and R 3a are as described above) The process of the compound (22a) shown

[0657] Process (23a) is to react the compound (22a) with a formula:

[0658] [Chemical formula 41]

[0659]

[0660] (In the formula, X a is as described above) The chlorosulfonic acid shown to obtain a formula:

[0661] [Chemical formula 42]

[0662]

[0663] (In the formula, R 1a , R 24a , R 3a and X a are as described above) The process of the compound (23a) shown

[0664] When R 1a contains a furan ring, for example, the furan ring can be opened by an acid and converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[0665] E a represents a leaving group. Examples of the above-mentioned leaving group include tert-butyldimethylsilyl (TBS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), benzyl (Bn), etc.

[0666] As R 22a , a linear or branched alkyl group having 1 or more carbon atoms is preferred, and methyl is more preferred.

[0667] As R 23a , a linear or branched alkyl group having 1 or more carbon atoms is preferred, and methyl is more preferred.

[0668] As R 24a , a linear or branched alkylene group having 1 or more carbon atoms is preferred, and methylene (-CH2-) is more preferred.

[0669] The reaction in step (21a) can be carried out in a solvent in the presence of a base.

[0670] Examples of the above base include sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, etc.

[0671] As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an alcohol or an ether is further preferred.

[0672] Examples of the above alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[0673] Examples of the above ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether, crown ethers (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0674] As the temperature of the reaction in step (21a), 0 to 40 °C is preferred, and 0 to 20 °C is more preferred.

[0675] As the pressure of the reaction in step (21a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0676] As the reaction time in step (21a), 0.1 hour to 72 hours is preferred, and 3 hours to 8 hours is more preferred.

[0677] The elimination reaction of the leaving group in step (22a) can be carried out by using fluoride ions or an acid. As the method for eliminating the leaving group, for example, the following methods can be cited: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF; a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0678] The elimination reaction of the leaving group in step (22a) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0679] Examples of the above ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether, crown ethers (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[0680] As the temperature of the reaction in step (22a), it is preferably 0 to 40 °C, more preferably 0 to 20 °C.

[0681] As the pressure of the reaction in step (22a), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[0682] As the reaction time in step (22a), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 8 hours.

[0683] In step (23a), as the reaction ratio of compound (22a) and the above-mentioned chlorosulfonic acid, considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (22a), the above-mentioned chlorosulfonic acid is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[0684] The reaction in step (23a) is preferably carried out in the presence of a base. Examples of the above base include alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc., and amines are preferred.

[0685] Examples of the above amine in step (23a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N',N'-tetramethyl-1,8-naphthalenediamine, etc., heteroaromatic amines such as pyridine, pyrrole, uracil, trimethylpyridine, dimethylpyridine, etc., and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. Among them, triethylamine and pyridine are preferred.

[0686] Regarding the dosage of the above base in step (23a), considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (22a), it is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[0687] The reaction in step (23a) can be carried out in a polar solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0688] Examples of the above ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ethers (15-crown-5, 18-crown-6), etc., and diethyl ether is preferred.

[0689] As the temperature of the reaction in step (23a), it is preferably 0 to 40 °C, more preferably 0 to 20 °C.

[0690] As the pressure of the reaction in step (23a), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[0691] As the reaction time in step (23a), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 12 hours.

[0692] When carrying out the reaction in step (23a) in a solvent, after the above reaction is terminated, a solution containing compound (23a) is obtained. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off, whereby high-purity compound (23a) can be recovered. When compound (23a) has a group represented by -OSO3H (i.e., when X is H), by using an aqueous alkali solution such as an aqueous sodium bicarbonate solution or ammonia water instead of water, -OSO3H can also be converted into a sulfate group.

[0693] After each step is terminated, the solvent can be distilled off or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[0694] Surfactant (a) can also be produced by a production method including the following steps (31a), (32a), (33a), and (34a), wherein

[0695] Step (31a) is to react a haloalkyl represented by the formula: Y a -R 3a -OE a

[0696] (wherein, R 3a As described above, Y a is a halogen atom, and E a is a leaving group) with an acetylene lithium represented by the formula:

[0697] [Chemical formula 43]

[0698]

[0699] (wherein, R 1a As described above) to obtain a compound (31a) represented by the formula:

[0700] [Chemical formula 44]

[0701]

[0702] (wherein, R 1a , R 3a and E a As described above) of the step,

[0703] Step (32a) is to oxidize compound (31a) to obtain the formula

[0704] [Chemical Formula 45]

[0705]

[0706] (In the formula, R 1a , R 3a and E a are as described above) The process of the compound (32a) shown

[0707] Process (33a) is to remove the leaving group possessed by the compound (32a) to obtain the formula:

[0708] [Chemical Formula 46]

[0709]

[0710] (In the formula, R 1a and R 3a are as described above) The process of the compound (33a) shown

[0711] Process (34a) is to react the compound (33a) with the formula:

[0712] [Chemical Formula 47]

[0713]

[0714] (In the formula, X a is as described above) The chlorosulfonic acid shown to obtain the formula:

[0715] [Chemical Formula 48]

[0716]

[0717] (In the formula, R 1a , R 3a and X a are as described above) The process of the compound (34a) shown

[0718] When R 1a contains a furan ring, for example, the furan ring can be opened with an acid to be converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[0719] E a represents a leaving group. Examples of the above-mentioned leaving group include tert-butyldimethylsilyl (TBS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), benzyl (Bn), etc.

[0720] In step (31a), considering the improvement of the yield and the reduction of waste, with respect to 1 mole of the above-mentioned haloalkyl, the above-mentioned lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles, as the reaction ratio of the above-mentioned haloalkyl and the above-mentioned lithium acetylide.

[0721] The reaction in step (31a) can be carried out in a solvent. As the above-mentioned solvent, hexane is preferred.

[0722] As the temperature of the reaction in step (31a), -100°C to -40°C is preferred, and -80°C to -50°C is more preferred.

[0723] As the pressure of the reaction in step (31a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0724] As the reaction time in step (31a), 0.1 hour to 72 hours is preferred, and 6 hours to 10 hours is more preferred.

[0725] The oxidation in step (32a) can be carried out as follows: After treating [(Cn * )Ru III (CF3CO2)3]·H2O (wherein Cn * represents 1,4,7-trimethyl-1,4,7-triazabicyclononane) with (NH4)2Ce(NO3)6 and trifluoroacetic acid, a complex is formed by adding sodium perchlorate, and the oxidation is carried out using this complex in a nitrile-based solvent.

[0726] After the oxidation is terminated, it can be neutralized with a base, and the compound (32a) is extracted using an organic solvent such as ether.

[0727] As the temperature of the reaction in step (32a), 30°C to 100°C is preferred, and 40°C to 90°C is more preferred.

[0728] As the pressure of the reaction in step (32a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0729] As the reaction time in step (32a), 0.1 hour to 72 hours is preferred, and 3 hours to 8 hours is more preferred.

[0730] The elimination reaction of the leaving group in step (33a) can be carried out by using a fluoride ion or an acid. As the method for eliminating the leaving group, for example, the following methods can be cited: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF; a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), or ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0731] The elimination reaction of the leaving group in step (33a) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0732] As the above ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether, crown ethers (15-crown-5, 18-crown-6), etc. can be mentioned. Among them, tetrahydrofuran and diethyl ether are preferred.

[0733] As the temperature of the reaction in step (33a), 0 to 40 °C is preferred, and 0 to 20 °C is more preferred.

[0734] As the pressure of the reaction in step (33a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0735] As the reaction time in step (33a), 0.1 hour to 72 hours is preferred, and 3 hours to 8 hours is more preferred.

[0736] In step (34a), as the reaction ratio of compound (33a) to the above chlorosulfonic acid, considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (33a), the above chlorosulfonic acid is preferably 1 mole to 2 moles, and more preferably 1 mole to 1.1 moles.

[0737] The reaction in step (34a) is preferably carried out in the presence of a base. As the above base, alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. can be mentioned. Among them, amines are preferred.

[0738] As the above amine in step (34a), tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, etc., heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, lutidine, etc., and cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. can be mentioned. Among them, triethylamine and pyridine are preferred.

[0739] Regarding the amount of the above base used in step (34a), considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (33a), it is preferably 1 mole to 2 moles, and more preferably 1 mole to 1.1 moles.

[0740] The reaction in step (34a) can be carried out in a polar solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0741] As the above-mentioned ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether, crown ether (15-crown-5, 18-crown-6), etc. can be cited, and among them, diethyl ether is preferred.

[0742] As the temperature of the reaction in step (34a), 0 to 40°C is preferred, and 0 to 20°C is more preferred.

[0743] As the pressure of the reaction in step (34a), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[0744] As the reaction time in step (34a), 0.1 hour to 72 hours is preferred, and 3 hours to 12 hours is more preferred.

[0745] When carrying out the reaction in step (34a) in a solvent, a solution containing compound (34a) is obtained after the above reaction is terminated. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off, whereby high-purity compound (34a) can be recovered. When compound (34a) has a group represented by -OSO3H (i.e., when X is H), by using an aqueous solution of a base such as an aqueous solution of sodium bicarbonate or ammonia water instead of water, -OSO3H can also be converted into a sulfate group.

[0746] After each step is terminated, the solvent can be distilled off or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[0747] The surfactant (a) can also be produced by a production method including step (41a) and step (42a), wherein,

[0748] Step (41a) is to react an olefin represented by the formula:

[0749] [Chemical formula 49]

[0750]

[0751] (wherein R 1a As described above, R 21a is a single bond or a divalent linking group) with an alkyne represented by the formula:

[0752] [Chemical formula 50]

[0753]

[0754] (wherein Y 51a is an alkoxy group) to obtain a compound represented by the formula:

[0755] [Chemical Formula 51]

[0756]

[0757] (wherein, R 1a and R 21a are as described above) The process of the compound (41a) shown

[0758] Process (42a) is to react the compound (41a) with a formula:

[0759] [Chemical Formula 52]

[0760]

[0761] (wherein, X a is as described above) The chlorosulfonic acid shown to obtain a formula:

[0762] [Chemical Formula 53]

[0763]

[0764] (wherein, R 1a , R 21a and X a are as described above) The process of the compound (42a) shown

[0765] When R 1a contains a furan ring, for example, the furan ring can be opened with an acid to be converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[0766] As R 21a , a single bond or a linear or branched alkylene group having 1 or more carbon atoms is preferred.

[0767] In process (41a), as the reaction ratio of the above-mentioned alkene to the above-mentioned alkyne, considering the improvement of the yield and the reduction of waste, relative to 1 mole of the above-mentioned alkyne, the above-mentioned alkene is preferably 0.5 mole to 2 moles, more preferably 0.6 mole to 1.2 moles.

[0768] The reaction in process (41a) is preferably carried out in the presence of a metal catalyst. Examples of the above-mentioned metal include ruthenium, etc.

[0769] Regarding the amount of the above-mentioned metal catalyst in process (41a), considering the improvement of the yield and the reduction of waste, relative to 1 mole of the above-mentioned alkene, it is preferably 0.01 mole to 0.4 mole, more preferably 0.05 mole to 0.1 mole.

[0770] The reaction in process (41a) can be carried out in a polar solvent. Examples of the above-mentioned solvent include water, acetonitrile, dimethylacetamide, dimethylformamide.

[0771] As the temperature of the reaction in step (41a), it is preferably 20°C to 160°C, more preferably 40°C to 140°C.

[0772] As the pressure of the reaction in step (41a), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[0773] As the reaction time in step (41a), it is preferably 0.1 hour to 72 hours, more preferably 4 hours to 8 hours.

[0774] In step (42a), as the reaction ratio of compound (41a) to the above-mentioned chlorosulfonic acid, considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (41a), the above-mentioned chlorosulfonic acid is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[0775] The reaction in step (42a) is preferably carried out in the presence of a base. As the above-mentioned base, alkali metal hydroxides, alkaline earth metal hydroxides, amines, etc. can be cited, and amines are preferred among them.

[0776] As the above-mentioned amine in step (42a), tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, N,N,N’,N’-tetramethyl-1,8-naphthalenediamine, etc., heteroaromatic amines such as pyridine, pyrrole, uracil, trimethylpyridine, dimethylpyridine, etc., cyclic amines such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, etc. can be cited. Among them, triethylamine and pyridine are preferred.

[0777] Regarding the dosage of the above-mentioned base in step (42a), considering the improvement of the yield and the reduction of waste, relative to 1 mole of compound (41a), it is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[0778] The reaction in step (42a) can be carried out in a polar solvent. As the above-mentioned solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[0779] As the above-mentioned ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ethers (15-crown-5, 18-crown-6), etc. can be cited. Among them, diethyl ether is preferred.

[0780] As the temperature of the reaction in step (42a), it is preferably 0 to 40°C, more preferably 0 to 20°C.

[0781] As the pressure of the reaction in step (42a), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[0782] As the reaction time in step (42a), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 12 hours.

[0783] When carrying out the reaction in step (42a) in a solvent, after the above reaction is terminated, a solution containing compound (42a) is obtained. After adding water to the above solution, it is allowed to stand and separated into two phases, the aqueous phase is recovered, and the solvent is distilled off, whereby high-purity compound (42a) can be recovered. When compound (42a) has a group represented by -OSO3H (i.e., when X is H), by using an aqueous alkali solution such as an aqueous sodium bicarbonate solution or ammonia water instead of water, -OSO3H can also be converted into a sulfate group.

[0784] After each step is terminated, the solvent can be distilled off or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[0785] Next, surfactant (b) will be described.

[0786] In formula (b), R 1b 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.

[0787] When the above alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may form a ring. As the above heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred. For example, a furan ring, etc. can be cited. In R 1b , the divalent heterocycle can be inserted between 2 carbon atoms, the divalent heterocycle can also be located at the end and bonded to -C(=O)-, and the monovalent heterocycle can be located at the end of the above alkyl group.

[0788] It should be noted that in this specification, the "number of carbon atoms" of the above alkyl group also includes the number of carbon atoms constituting the above heterocycle.

[0789] Regarding the above substituents that the above alkyl group as R 1b can have, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxyl group are preferred, and methyl and ethyl are particularly preferred.

[0790] As the above alkyl group of R 1b it is preferably free of a carbonyl group.

[0791] In the above alkyl groups, 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, but preferably they are non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0792] The above alkyl group preferably has no substituents.

[0793] As R 1b , it is preferably a linear or branched alkyl group having 1 to 10 carbon atoms with or without substituents or a cyclic alkyl group having 3 to 10 carbon atoms with or without substituents, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms that does not contain a carbonyl group, further preferably a linear or branched alkyl group having 1 to 10 carbon atoms without substituents, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms without substituents, particularly preferably methyl (-CH3) or ethyl (-C2H5), and most preferably methyl (-CH3).

[0794] In formula (b), R 2b and R 4b are independently H or a substituent. Two or more R 2b and R 4b may be the same or different respectively.

[0795] Regarding the above substituents as R 2b and R 4b , preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, particularly preferably methyl or ethyl.

[0796] As the above alkyl groups of R 2b and R 4b , they preferably do not contain a carbonyl group. In the above alkyl groups, 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, but preferably they are non-halogenated alkyl groups that do not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0797] The above alkyl group preferably has no substituents.

[0798] Regarding the above as R 2b and R 4bThe above-mentioned alkyl group preferably refers to a linear or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group with 3 to 10 carbon atoms that does not contain a carbonyl group. More preferably, it is a linear or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group. Further preferably, it is a linear or branched alkyl group with 1 to 3 carbon atoms that does not have a substituent. Particularly preferably, it is methyl (-CH3) or ethyl (-C2H5).

[0799] As R 2b and R 4b , they are preferably independently H or a linear or branched alkyl group with 1 to 10 carbon atoms that does not contain a carbonyl group. More preferably, they are H or a linear or branched alkyl group with 1 to 3 carbon atoms that does not have a substituent. Still more preferably, they are H, methyl (-CH3) or ethyl (-C2H5). Particularly preferably, it is H.

[0800] In formula (b), R 3b is an alkylene group with 1 to 10 carbon atoms that may or may not have a substituent. When there are two or more R 3b , they may be the same or different.

[0801] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0802] In the above-mentioned alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, 25% or less may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0803] The above-mentioned alkylene group preferably does not have any substituents.

[0804] As the above-mentioned alkylene group, preferably a linear or branched alkylene group with 1 to 10 carbon atoms that may or may not have a substituent or a cyclic alkylene group with 3 to 10 carbon atoms that may or may not have a substituent. More preferably, it is a linear or branched alkylene group with 1 to 10 carbon atoms that does not contain a carbonyl group or a cyclic alkylene group with 3 to 10 carbon atoms that does not contain a carbonyl group. More preferably, it is a linear or branched alkylene group with 1 to 10 carbon atoms that does not have a substituent. Further preferably, it is methylene (-CH2-), ethylene (-C2H4-), isopropylidene (-CH(CH3)CH2-) or propylene (-C3H6-).

[0805] R 1b 、R 2b 、R 3b and R 4b Any two of them may be bonded to each other to form a ring, but it is preferably not to form a ring.

[0806] In formula (b), n is an integer of 1 or more. As n, an integer of 1 to 40 is preferred, an integer of 1 to 30 is more preferred, an integer of 5 to 25 is further preferred, and an integer of 5 to 9 or 11 to 25 is particularly preferred.

[0807] In formula (b), p and q are independently integers of 0 or more. As p, an integer of 0 to 10 is preferred, and 0 or 1 is more preferred. As q, an integer of 0 to 10 is preferred, and an integer of 0 to 5 is more preferred.

[0808] The sum of n, p, and q is preferably an integer of 5 or more. The sum of n, p, and q is more preferably an integer of 8 or more. The sum of n, p, and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and further preferably an integer of 40 or less.

[0809] In formula (b), X b is H, a metal atom, NR 5b 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, and R 5b is H or an organic group. The four Rs 5b may be the same or different. As the organic group in R 5b , an alkyl group is preferred. As R 5b , H or an organic group having 1 to 10 carbon atoms is preferred, H or an organic group having 1 to 4 carbon atoms is more preferred, and H or an alkyl group having 1 to 4 carbon atoms is further preferred. As the above metal atom, a monovalent or divalent metal atom can be mentioned, such as an alkali metal (Group 1) or an alkaline earth metal (Group 2), and Na, K, or Li is preferred. X b can be a metal atom or NR 5b 4 (R 5b as described above).

[0810] As X b , H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR 5b 4 is preferred. For the reason of being easily soluble in water, H, Na, K, Li, or NH4 is more preferred. For the reason of being more easily soluble in water, Na, K, or NH4 is further preferred. Na or NH4 is particularly preferred. For the reason of being easily removed, NH4 is most preferred. When X b is NH4, the above surfactant has excellent solubility in an aqueous medium and is not likely to leave a metal component in PTFE or the final product.

[0811] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6bCO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 the carbonyl group contained in CO-B-, B is a single bond or an alkylene group with 1 to 10 carbon atoms with or without substituents, R 6b is H or an alkyl group with 1 to 4 carbon atoms with or without substituents. The number of carbon atoms of the above alkylene group is more preferably 1 to 5. In addition, the above R 6 is more preferably H or methyl. * refers to the side bonded to -OSO3X in the formula b bonded side.

[0812] L is preferably a single bond.

[0813] As the surfactant (b), the following formula is preferred:

[0814] [Chemical formula 54]

[0815]

[0816] (In the formula, R 1b , R 2b , L, n and X b are as described above) the compound shown.

[0817] The above surfactant (b) in 1 The integrated value of all peak intensities observed in the H-NMR spectrum in the region of 2.0 ppm to 5.0 ppm is preferably 10% or more.

[0818] The above surfactant (b) in 1 The integrated value of all peak intensities observed in the H-NMR spectrum in the region of 2.0 ppm to 5.0 ppm is preferably within the above range. In this case, the above surfactant preferably has a ketone structure in the molecule.

[0819] In the above surfactant (b), the above integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and further preferably 70 or less.

[0820] The above integrated value is measured at room temperature using a deuterium oxide solvent. The deuterium oxide is 4.79 ppm.

[0821] As the surfactant (b), for example,

[0822] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0823] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0824] CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0825] CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na,

[0826] CH3C(O)CH2CH2CH2CH2CH2OSO3Na,

[0827] CH3C(O)CH2CH2CH2CH2OSO3Na,

[0828] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0829] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0830] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0831] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0832] CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0833] CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na,

[0834] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na,

[0835] CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na,

[0836] CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na,

[0837] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na,

[0838] CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na、

[0839] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na、

[0840] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na、

[0841] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na、

[0842] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na、

[0843] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na、

[0844] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na、

[0845] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、

[0846] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li、

[0847] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、

[0848] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、

[0849] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na、

[0850] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0851] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0852] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0853] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0854] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0855] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0856] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0857] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0858] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0859] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0860] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0861] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、

[0862] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0863] CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na,

[0864] CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na,

[0865] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na,

[0866] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na,

[0867] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na,

[0868] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na,

[0869] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na,

[0870] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na,

[0871] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H,

[0872] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li,

[0873] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K,

[0874] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4,

[0875] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, etc.

[0876] The surfactant (b) is a new compound and can be produced, for example, by the production methods exemplified below.

[0877] The surfactant (b) can be produced by a production method including step (11b), step (12b), and step (13b), where

[0878] Step (11b) is to use the following formula:

[0879] R 11b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH

[0880] (In the formula, R 2b ~R 4b , n, p, and q are as described above. R 11b is H, 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. 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 a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b(The carbonyl group contained in CO-B), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without substituents, R 6b is H or an alkyl group having 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to -OH in the formula) The compound (10b) shown is hydroxylated to obtain the following formula:

[0881] [Chemical formula 55]

[0882]

[0883] (In the formula, L, R 2b ~R 4b 、R 11b 、n, p and q are as described above) The process of the compound (11b) shown,

[0884] Process (12b) is to oxidize the compound (11b) to obtain the following formula:

[0885] [Chemical formula 56]

[0886]

[0887] (In the formula, L, R 2b ~R 4b 、R 11b 、n, p and q are as described above) The process of the compound (12b) shown,

[0888] Process (13b) is to sulfuric acid esterify the compound (12b) to obtain the following formula:

[0889] [Chemical formula 57]

[0890]

[0891] (In the formula, L, R 2b ~R 4b 、R 11b 、n, p, q and X b are as described above) The process of the compound (13b) shown.

[0892] As the above alkyl group of R 11b Preferably, it does not contain a carbonyl group.

[0893] As the above alkyl group of R 11b In, up to 75% of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, up to 50% can be substituted by halogen atoms, up to 25% can be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group without halogen atoms such as fluorine atoms and chlorine atoms.

[0894] The above alkyl group preferably does not have any substituents.

[0895] As R 11b , preferably H, a linear or branched alkyl group having 1 to 9 carbon atoms with or without substituents, or a cyclic alkyl group having 3 to 9 carbon atoms with or without substituents, more preferably H, a linear or branched alkyl group having 1 to 9 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 9 carbon atoms not containing a carbonyl group, further preferably H, or a linear or branched alkyl group having 1 to 9 carbon atoms without substituents, still more preferably H, methyl (-CH3) or ethyl (-C2H5), particularly preferably H or methyl (-CH3), and most preferably H.

[0896] The hydroxylation in step (11b) can be carried out, for example, by the following methods: (1) a method of reacting iron(II) phthalocyanine (Fe(Pc)) and sodium borohydride in an oxygen atmosphere with compound (10b); (2) a method of reacting isopinocampheylborane (IpcBH2) with compound (10b) and then oxidizing the resulting intermediate (dialkylboron).

[0897] In method (1), the amount of iron(II) phthalocyanine can be a catalytic amount and can be used in an amount of 0.001 mol to 1.2 mol relative to 1 mol of compound (10b).

[0898] In method (1), relative to 1 mol of compound (10b), sodium borohydride can be used in an amount of 0.5 mol to 20 mol.

[0899] The reaction of method (1) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, nitrogen-containing polar organic compounds, etc.

[0900] As the above ether, examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferred.

[0901] As the above halogenated hydrocarbon, examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferred.

[0902] As the above aromatic hydrocarbon, examples include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferred.

[0903] As the above nitrile, examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and among them, acetonitrile is preferred.

[0904] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0905] As the reaction temperature of method (1), -78°C to 200°C is preferred, and 0 to 150°C is more preferred.

[0906] As the reaction pressure of method (1), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[0907] As the reaction time of method (1), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[0908] In method (2), per 1 mole of compound (10b), isopinocampheylborane can be used in an amount of 1.0 mole to 10.0 moles.

[0909] The reaction of compound (10b) with isopinocampheylborane can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and examples include ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[0910] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[0911] Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[0912] Examples of the above aromatic hydrocarbon include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[0913] As the reaction temperature of the reaction of compound (10b) with isopinocampheylborane, -78°C to 200°C is preferred, and 0 to 150°C is more preferred.

[0914] As the reaction pressure of the reaction of compound (10b) with isopinocampheylborane, 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[0915] As the reaction time of the reaction of compound (10b) with isopinocampheylborane, 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[0916] The oxidation in method (2) can be carried out by allowing an oxidizing agent to act on the above intermediate. Examples of the above oxidizing agent include hydrogen peroxide. The above oxidizing agent can be used in an amount of 0.7 mol to 10 mol relative to 1 mol of the above intermediate.

[0917] The oxidation in method (2) can be carried out in a solvent. Examples of the above solvent include water, methanol, ethanol, etc., and water is preferred.

[0918] As the temperature of the oxidation in method (2), 0 to 100 °C is preferred, and 0 to 80 °C is more preferred.

[0919] As the pressure of the oxidation in method (2), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[0920] As the time of the oxidation in method (2), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[0921] In step (12b), examples of the method for oxidizing compound (11b) include: (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation); (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method in which a bleaching agent (about 5 to 6% aqueous solution of NaOCl) acts in the presence of a nickel compound such as NiCl2; (e) a method in which a hydrogen acceptor such as an aldehyde or a ketone acts in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0922] The oxidation in step (12b) can be carried out in a solvent. As the above solvent, water and organic solvents are preferred, and examples include water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, etc.

[0923] Examples of the above ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc., and acetone is preferred.

[0924] Examples of the above ethers include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and diethyl ether and tetrahydrofuran are preferred.

[0925] Examples of the above halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and dichloromethane and chloroform are preferred.

[0926] Examples of the above aromatic hydrocarbons include benzene, toluene, xylene, etc., and benzene and toluene are preferred.

[0927] As the above-mentioned nitrile, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. can be mentioned, among which acetonitrile is preferred.

[0928] As the temperature of oxidation in step (12b), -78°C to 200°C is preferred, and it can be appropriately selected according to the method adopted.

[0929] As the pressure of oxidation in step (12b), 0 to 5.0 MPa is preferred, and it can be appropriately selected according to the method adopted.

[0930] As the time of oxidation in step (12b), 0.1 hour to 72 hours is preferred, and it can be appropriately selected according to the method adopted.

[0931] The sulfation in step (13b) can be carried out by reacting compound (12b) with a sulfating agent. As the above-mentioned sulfating agent, sulfur trioxide pyridine complex, sulfur trioxide trimethylamine complex, sulfur trioxide triethylamine complex and other sulfur trioxide amine complexes, sulfur trioxide dimethylformamide complex and other sulfur trioxide amide complexes, sulfuric acid - dicyclohexylcarbodiimide, chlorosulfuric acid, concentrated sulfuric acid, sulfamic acid, etc. can be mentioned. As the dosage of the above-mentioned sulfating agent, relative to 1 mole of compound (12b), it is preferably 0.5 mole to 10 moles, more preferably 0.5 mole to 5 moles, and further preferably 0.7 mole to 4 moles.

[0932] The sulfation in step (13b) can be carried out in a solvent. As the above-mentioned solvent, an organic solvent is preferred, and ether, halogenated hydrocarbon, aromatic hydrocarbon, pyridine, dimethyl sulfoxide, sulfolane, nitrile, etc. can be mentioned.

[0933] As the above-mentioned ether, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be mentioned, among which diethyl ether and tetrahydrofuran are preferred.

[0934] As the above-mentioned halogenated hydrocarbon, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be mentioned, among which dichloromethane and chloroform are preferred.

[0935] As the above-mentioned aromatic hydrocarbon, benzene, toluene, xylene, etc. can be mentioned, among which benzene and toluene are preferred.

[0936] As the above-mentioned nitrile, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. can be mentioned, among which acetonitrile is preferred.

[0937] As the temperature of sulfation in step (13b), -78°C to 200°C is preferred, and -20°C to 150°C is more preferred.

[0938] As the pressure of sulfation in step (13b), 0 to 10 MPa is preferred, and 0.1 MPa to 5 MPa is more preferred.

[0939] As the time for sulfation in step (13b), it is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0940] The surfactant (b) can also be produced by a production method including step (21b) and step (22b), where

[0941] Step (21b) is to subject the following formula:

[0942] [Chemical formula 58]

[0943]

[0944] (In the formula, L, R 1b ~R 4b , n, p and q are as described above. R 101b is an organic group) of the compound (20b) to ozonolysis to obtain the following formula:

[0945] [Chemical formula 59]

[0946]

[0947] (In the formula, L, R 1b ~R 4b , n, p and q are as described above) of the compound (21b) of the step,

[0948] Step (22b) is to subject the compound (21b) to sulfation to obtain the following formula:

[0949] [Chemical formula 60]

[0950]

[0951] (In the formula, L, R 1b ~R 4b , n, p, q and X b are as described above) of the compound (22b) of the step.

[0952] As R 101b , an alkyl group having 1 to 20 carbon atoms is preferred. Two R 101b may be the same or different.

[0953] The ozonolysis in step (21b) can be carried out by allowing ozone to act on the compound (20b) and then performing post-treatment with a reducing agent.

[0954] Ozone can be generated by silent discharge in oxygen.

[0955] Examples of the reducing agent used in the above post-treatment include zinc, dimethyl sulfide, thiourea, phosphines, etc., and phosphines are preferred.

[0956] The ozonolysis in step (21b) can be carried out in a solvent. As the above-mentioned solvent, water and organic solvents are preferred, and examples thereof include water, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[0957] As the above-mentioned alcohols, methanol, ethanol, 1-propanol, isopropanol, etc. can be cited. Among them, methanol and ethanol are preferred.

[0958] As the above-mentioned carboxylic acids, acetic acid, propionic acid, etc. can be cited. Among them, acetic acid is preferred.

[0959] As the above-mentioned ethers, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be cited. Among them, diethyl ether and tetrahydrofuran are preferred.

[0960] As the above-mentioned halogenated hydrocarbons, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be cited. Among them, dichloromethane and chloroform are preferred.

[0961] As the above-mentioned aromatic hydrocarbons, benzene, toluene, xylene, etc. can be cited. Among them, benzene and toluene are preferred.

[0962] As the temperature of the ozonolysis in step (21b), -78°C to 200°C is preferred, and 0 to 150°C is more preferred.

[0963] As the pressure of the ozonolysis in step (21b), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[0964] As the time of the ozonolysis in step (21b), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[0965] The sulfation in step (22b) can be carried out by reacting compound (21b) with a sulfating agent, and the same conditions as those in the sulfation in step (13b) can be adopted.

[0966] Surfactant (b) can also be manufactured by a manufacturing method including step (31b), step (32b), step (33b) and step (34b), wherein,

[0967] Step (31b) is to use the following formula:

[0968] R 21b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH

[0969] (wherein L, R 2b ~R 4b , n, p, and q are as described above. R 21b is H, 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. When having 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring) The compound (30b) shown by the following formula is epoxidized to obtain the following formula:

[0970] [Chemical formula 61]

[0971]

[0972] (wherein L, R 2b ~R 4b , R 21b , n, p, and q are as described above) The step of the compound (31b) shown by the following formula,

[0973] Step (32b) is to react the compound (31b) with R 22b 2CuLi (R 22b 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. When having 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring) The dialkylcopper lithium shown by the following formula is reacted to obtain the following formula:

[0974] [Chemical formula 62]

[0975]

[0976] (wherein L, R 2b ~R 4b , R 21b , R 22b , n, p, and q are as described above) The step of the compound (32b) shown by the following formula,

[0977] Step (33b) is to oxidize the compound (32b) to obtain the following formula:

[0978] [Chemical formula 63]

[0979]

[0980] (wherein L, R 2b ~R 4b , R 21b , R 22b , n, p, and q are as described above) The step of the compound (33b) shown by the following formula,

[0981] Step (34b) is to sulfonate compound (33b) to obtain the following formula:

[0982] [Chemical formula 64]

[0983]

[0984] (In the formula, L, R 2b ~R 4b 、R 21b 、R 22b 、n, p, q and X b are as described above) is the step of compound (34b).

[0985] As the above-mentioned alkyl group for R 21b preferably does not contain a carbonyl group.

[0986] In the above-mentioned alkyl group for R 21b up to 75% of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, up to 50% can be substituted by halogen atoms, up to 25% can be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0987] The above-mentioned alkyl group preferably does not have any substituents.

[0988] As R 21b , preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms with or without substituents, or a cyclic alkyl group having 3 to 8 carbon atoms with or without substituents, more preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group, further preferably H, or a linear or branched alkyl group having 1 to 8 carbon atoms that does not have substituents, particularly preferably H or methyl (-CH3), and most preferably H.

[0989] As the above-mentioned alkyl group for R 22b preferably does not contain a carbonyl group.

[0990] As the above-mentioned alkyl group for R 22b up to 75% of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, up to 50% can be substituted by halogen atoms, up to 25% can be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0991] The above-mentioned alkyl group preferably does not have any substituents.

[0992] As R 22b, preferably a linear or branched alkyl group having 1 to 9 carbon atoms with or without substituents, or a cyclic alkyl group having 3 to 9 carbon atoms with or without substituents, more preferably a linear or branched alkyl group having 1 to 9 carbon atoms without a carbonyl group or a cyclic alkyl group having 3 to 9 carbon atoms without a carbonyl group, further preferably a linear or branched alkyl group having 1 to 9 carbon atoms without substituents, particularly preferably methyl (-CH3) or ethyl (-C2H5), and most preferably methyl (-CH3).

[0993] Two Rs 22b may be the same or different.

[0994] R 21b and R 22b preferably have a total of 1 to 7 carbon atoms, more preferably 1 to 2 carbon atoms, and most preferably 1 carbon atom.

[0995] The epoxidation in step (31b) can be carried out by reacting an epoxidizing agent with compound (30b).

[0996] Examples of the above epoxidizing agent include m-chloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, peracids such as tert-butyl hydroperoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, etc. Among them, peracids are preferred, and m-chloroperbenzoic acid is more preferred.

[0997] Relative to 1 mole of compound (30b), the above epoxidizing agent can be used in an amount of 0.5 mole to 10.0 moles.

[0998] The epoxidation in step (31b) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and examples include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridine, nitrogen-containing polar organic compounds, dimethyl sulfoxide, etc. Among them, dichloromethane is preferred.

[0999] Examples of the above ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[1000] Examples of the above ethers include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[1001] Examples of the above halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[1002] Examples of the above aromatic hydrocarbons include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[1003] Examples of the above nitriles include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. Among them, acetonitrile is preferred.

[1004] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc., and among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[1005] As the temperature for epoxidation in step (31b), -78°C to 200°C is preferred, and -40°C to 150°C is more preferred.

[1006] As the pressure for epoxidation in step (31b), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[1007] As the time for epoxidation in step (31b), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[1008] In step (32b), relative to 1 mole of compound (31b), the dialkylcopper lithium can be used in an amount of 0.5 mole to 10.0 moles.

[1009] The reaction of step (32b) can be carried out in a solvent. As the solvent, an organic solvent is preferred, and examples include ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[1010] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferred.

[1011] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferred.

[1012] Examples of the aromatic hydrocarbon include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferred.

[1013] As the temperature of the reaction in step (32b), -78°C to 200°C is preferred, and -40°C to 150°C is more preferred.

[1014] As the pressure of the reaction in step (32b), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[1015] As the time of the reaction in step (32b), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[1016] In step (33b), as a method for oxidizing compound (32b), for example, the following methods can be mentioned: (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation); (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method in which a bleaching agent (an approximately 5-6% aqueous solution of NaOCl) is allowed to act in the presence of a nickel compound such as NiCl2; (e) a method in which a hydrogen acceptor such as an aldehyde or a ketone is allowed to act in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[1017] The oxidation in step (33b) can be carried out in a solvent. As the above-mentioned solvent, water and organic solvents are preferred, and examples thereof include water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, etc.

[1018] As the above-mentioned ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. can be mentioned, and among them, acetone is preferred.

[1019] As the above-mentioned alcohols, methanol, ethanol, 1-propanol, isopropyl alcohol, etc. can be mentioned. Among them, methanol and ethanol are preferred.

[1020] As the above-mentioned ethers, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be mentioned, and among them, diethyl ether and tetrahydrofuran are preferred.

[1021] As the above-mentioned halogenated hydrocarbons, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be mentioned, and among them, dichloromethane and chloroform are preferred.

[1022] As the above-mentioned aromatic hydrocarbons, benzene, toluene, xylene, etc. can be mentioned, and among them, benzene and toluene are preferred.

[1023] As the above-mentioned nitriles, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. can be mentioned, and among them, acetonitrile is preferred.

[1024] As the temperature of the oxidation in step (33b), -78°C to 200°C is preferred, and it can be appropriately selected according to the method adopted.

[1025] As the pressure of the oxidation in step (33b), 0 to 5.0 MPa is preferred, and it can be appropriately selected according to the method adopted.

[1026] As the time of the oxidation in step (33b), 0.1 hour to 72 hours is preferred, and it can be appropriately selected according to the method adopted.

[1027] The sulfation in step (34b) can be carried out by reacting compound (33b) with a sulfating agent, and the same conditions as those in the sulfation in step (13b) can be adopted.

[1028] The surfactant (b) can also be produced by a production method including step (41b) and step (42b), where

[1029] Step (41b) is to oxidize the following formula:

[1030] R 11b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH

[1031] (wherein, L, R 2b ~R 4b 、R 11b 、n, p and q are as described above) to obtain the following formula:

[1032] [Chemical formula 65]

[1033]

[1034] (wherein, L, R 2b ~R 4b 、R 11b 、n, p and q are as described above) to obtain the compound (41b) of the step,

[1035] Step (42b) is to sulfonate the compound (41b) to obtain the following formula:

[1036] [Chemical formula 66]

[1037]

[1038] (wherein, L, R 2b ~R 4b 、R 11b 、n, p, q and X b are as described above) to obtain the compound (42b) of the step.

[1039] The oxidation in step (41b) can be carried out by allowing an oxidizing agent to act on the compound (10b) in the presence of water and a palladium compound.

[1040] As the above-mentioned oxidizing agent, cuprous or cupric salts such as copper chloride, copper acetate, copper cyanide, copper trifluoromethanethiolate, ferric salts such as ferric chloride, ferric acetate, ferric cyanide, ferric trifluoromethanethiolate, hexacyanoferrate, quinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, H2O2, MnO2, KMnO4, RuO4, m-chloroperbenzoic acid, oxygen, etc. can be cited. Among them, cuprous salts, ferric salts, and quinones are preferred, and copper chloride, ferric chloride, and 1,4-benzoquinone are more preferred.

[1041] Relative to 1 mole of the compound (10b), the above-mentioned oxidizing agent can be used in an amount of 0.001 mole to 10 moles.

[1042] Relative to 1 mole of the compound (10b), the above-mentioned water can be used in an amount of 0.5 mole to 1000 moles.

[1043] As the above-mentioned palladium compound, palladium dichloride can be cited. The amount of the above-mentioned palladium compound can be a catalytic amount, and relative to 1 mole of the compound (10b), it can be used in an amount of 0.0001 mole to 1.0 mole.

[1044] The oxidation in the step (41b) can be carried out in a solvent. As the above-mentioned solvent, water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, sulfolane can be cited.

[1045] As the above-mentioned esters, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-acetoxypropane), etc. can be cited, and ethyl acetate is preferred among them.

[1046] As the above-mentioned aliphatic hydrocarbons, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral essential oil, etc. can be cited, and cyclohexane and heptane are preferred among them.

[1047] As the above-mentioned aromatic hydrocarbons, benzene, toluene, xylene, etc. can be cited, and benzene and toluene are preferred among them.

[1048] As the above-mentioned alcohols, methanol, ethanol, 1-propanol, isopropanol, etc. can be cited.

[1049] As the above-mentioned carboxylic acids, acetic acid, propionic acid, etc. can be cited. Acetic acid is preferred among them.

[1050] As the above-mentioned ethers, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be cited, and diethyl ether and tetrahydrofuran are preferred among them.

[1051] As the above-mentioned halogenated hydrocarbon, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be cited, among which dichloromethane and chloroform are preferred.

[1052] As the above-mentioned nitrogen-containing polar organic compound, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. can be cited, among which N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[1053] As the above-mentioned nitrile, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. can be cited, among which acetonitrile is preferred.

[1054] As the temperature of the oxidation in step (41b), -78°C to 200°C is preferred, and -20°C to 150°C is more preferred.

[1055] As the pressure of the oxidation in step (41b), 0 to 10 MPa is preferred, and 0.1 MPa to 5.0 MPa is more preferred.

[1056] As the time of the oxidation in step (41b), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[1057] The sulfuric acid esterification in step (42b) can be carried out by reacting compound (41b) with a sulfuric acid reagent, and the same conditions as those in the sulfuric acid esterification in step (13b) can be adopted.

[1058] Surfactant (b) can also be manufactured by a manufacturing method including step (51), step (52), step (53), and step (54), wherein,

[1059] Step (51) is to react a compound (50) represented by the following formula:

[1060] R 11b -CH=CH-(CR 2b 2) n -OH

[1061] (In the formula, R 2b , R 11b and n are as described above) with a halogenating agent to obtain a compound represented by the following formula:

[1062] R 11b -CH=CH-(CR 2b 2) n -Z 51b

[1063] (In the formula, R 2b , R 11b and n are as described above. Z 51bThe process for the compound (51) (where Z is a halogen atom).

[1064] Process (52) is to react the compound (51) with HO-R 3b -L-OH (L and R are as described above) with an alkylene glycol to obtain the following formula: 3b

[1065] R 11b -CH=CH-(CR 2b 2) n -O-R 3b -L-OH

[1066] (wherein L, R 2b , R 3b , R 11b and n are as described above) to obtain the compound (52).

[1067] Process (53) is to oxidize the compound (52) to obtain the following formula:

[1068] [Chemical Formula 67]

[1069]

[1070] (wherein L, R 2b , R 3b , R 11b and n are as described above) to obtain the compound (53).

[1071] Process (54) is to sulfonate the compound (53) to obtain the following formula:

[1072] [Chemical Formula 68]

[1073]

[1074] (wherein L, R 2b , R 3b , R 11b , n and X b are as described above) to obtain the compound (54).

[1075] As Z, F, Cl, Br or I is preferred, and Br is more preferred. 51b

[1076] As the halogenating agent used in process (51), N-bromosuccinimide, N-chlorosuccinimide, etc. can be cited.

[1077]

[1078] Relative to 1 mole of the compound (50), the above halogenating agent can be used in an amount of 0.5 mole to 10.0 moles.

[1078] The reaction of step (51) can be carried out in the presence of a phosphine such as triphenylphosphine.

[1079] Per 1 mole of compound (50), the above-mentioned phosphine can be used in an amount of 0.5 mole to 10.0 moles.

[1080] The reaction of step (51) can be carried out in a solvent. As the above-mentioned solvent, an organic solvent is preferred, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[1081] As the above-mentioned ether, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be cited, and among them, diethyl ether and tetrahydrofuran are preferred.

[1082] As the above-mentioned halogenated hydrocarbon, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be cited, and among them, dichloromethane and chloroform are preferred.

[1083] As the above-mentioned aromatic hydrocarbon, benzene, toluene, xylene, etc. can be cited, and among them, benzene and toluene are preferred.

[1084] As the temperature of the reaction in step (51), -78 °C to 200 °C is preferred, and -40 °C to 150 °C is more preferred.

[1085] As the pressure of the reaction in step (51), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[1086] As the reaction time in step (51), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[1087] In step (52), per 1 mole of compound (51), the above-mentioned alkylene glycol can be used in an amount of 0.5 mole to 10.0 moles.

[1088] The reaction of step (52) can be carried out in the presence of a base. As the above-mentioned base, sodium hydride, sodium hydroxide, potassium hydroxide, etc. can be cited.

[1089] Per 1 mole of compound (51), the above-mentioned base can be used in an amount of 0.5 mole to 10.0 moles.

[1090] The reaction of step (52) can be carried out in a solvent. As the above-mentioned solvent, an organic solvent is preferred, and examples thereof include nitrogen-containing polar organic compounds, ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[1091] As the above-mentioned nitrogen-containing polar organic compound, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. can be cited, and among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[1092] Examples of the above-mentioned ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and diethyl ether and tetrahydrofuran are preferred.

[1093] Examples of the above-mentioned halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and dichloromethane and chloroform are preferred.

[1094] Examples of the above-mentioned aromatic hydrocarbon include benzene, toluene, xylene, etc., and benzene and toluene are preferred.

[1095] As the temperature of the reaction in step (52), -78°C to 200°C is preferred, and -40°C to 150°C is more preferred.

[1096] As the pressure of the reaction in step (52), 0 to 5.0 MPa is preferred, and 0.1 MPa to 1.0 MPa is more preferred.

[1097] As the reaction time of step (52), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[1098] The oxidation in step (53) can be carried out by allowing an oxidizing agent to act on compound (52) in the presence of water and a palladium compound, and the same conditions as those in the oxidation in step (41) can be adopted.

[1099] The sulfation in step (54) can be carried out by reacting compound (53) with a sulfating agent, and the same conditions as those in the sulfation in step (13) can be adopted.

[1100] In any of the above manufacturing methods, after each step is completed, the solvent can be removed by distillation or distillation, purification, etc. can be carried out to improve the purity of the obtained compound. In addition, when the obtained compound has a group represented by -OSO3H (i.e., when X b is H), -OSO3H can be converted into a sulfate group by contacting with a base such as sodium carbonate or ammonia.

[1101] In the manufacturing method of surfactant (b), the manufacturing method including the above steps (41b) and (42b) is preferred.

[1102] Surfactant (c) will be described.

[1103] In formula (c), R 1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[1104] When the number of carbon atoms of the above-mentioned alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be included between two carbon atoms. In addition, when the number of carbon atoms of the above-mentioned alkyl group is 2 or more, the above-mentioned carbonyl group may also be included at the end of the above-mentioned alkyl group. That is, acyl groups such as acetyl group represented by CH3-C(=O)- are also included in the above-mentioned alkyl group.

[1105] In addition, when the number of carbon atoms of the above-mentioned alkyl group is 3 or more, a monovalent or divalent heterocycle may be included, or a ring may be formed. As the above-mentioned heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred. For example, a furan ring etc. can be cited. In R 1c , the divalent heterocycle can be inserted between two carbon atoms, the divalent heterocycle can also be located at the end and bonded to -C(=O)-, and the monovalent heterocycle can be located at the end of the above-mentioned alkyl group.

[1106] It should be noted that in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocycle. For example, the number of carbon atoms of the group represented by CH3-C(=O)-CH2- is 3, the number of carbon atoms of the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- is 7, and the number of carbon atoms of the group represented by CH3-C(=O)- is 2.

[1107] In the above-mentioned alkyl group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group. For example, it may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group.

[1108] As the above-mentioned monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 101c (wherein, R 101c is an alkyl group) can be cited.

[1109] In the above-mentioned alkyl group, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, 25% or less may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[1110] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group.

[1111] R 2c and R 3c are preferably independently a single bond or a linear or branched alkylene group having 1 or more carbon atoms or a cyclic alkylene group having 3 or more carbon atoms.

[1112] Constituting R 2c and R 3cThe above-mentioned alkylene preferably does not contain a carbonyl group.

[1113] In the above-mentioned alkylene, a hydrogen atom bonded to a carbon atom may be substituted by a functional group, for example, it may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group.

[1114] As the above-mentioned monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 102c (In the formula, R 102c is an alkyl group) can be cited.

[1115] In the above-mentioned alkylene, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, 25% or less may be substituted by halogen atoms, but it is preferably a non-halogenated alkylene that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[1116] R 1c , R 2c and R 3c The total number of carbon atoms is 5 or more. As the total number of carbon atoms, it is preferably 7 or more, more preferably 9 or more, preferably 20 or less, more preferably 18 or less, and further preferably 15 or less.

[1117] R 1c , R 2c and R 3c Any two of them may be bonded to each other to form a ring.

[1118] In formula (c), A in the formula c is -COOX c or -SO3X c (X c is H, a metal atom, NR 4c 4, an imidazolium with or without substituents, a pyridinium with or without substituents, or a phosphonium with or without substituents, R 4c is H or an organic group, and may be the same or different). As the organic group in R 4c , an alkyl group is preferred. As R 4c , H or an organic group having 1 to 10 carbon atoms is preferred, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. As the above-mentioned metal atom, a monovalent or divalent metal atom can be cited, and an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be cited, and Na, K or Li is preferred.

[1119] As X c , H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 4c4. For reasons of high solubility in water, H, Na, K, Li or NH4 is more preferred; for reasons of even higher solubility in water, Na, K or NH4 is further preferred; Na or NH4 is particularly preferred; and NH4 is most preferred for reasons of easy removal. X c When X is NH4, the above surfactant has excellent solubility in an aqueous medium and is not likely to leave metal components in PTFE or the final product.

[1120] As R 1c , a linear or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms and containing a monovalent or divalent heterocyclic ring is preferred.

[1121] In addition, as R 1c , the following formula is more preferred:

[1122] [Chemical formula 69]

[1123]

[1124] (In the formula, n 11c is an integer from 0 to 10, R 11c is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R 12c is an alkylene group having 0 to 3 carbon atoms. When n 11c is an integer from 2 to 10, R 12c can be the same or different from each other)

[1125] As n 11c , an integer from 0 to 5 is preferred, an integer from 0 to 3 is more preferred, and an integer from 1 to 3 is further preferred.

[1126] As the above alkyl group of R 11c , it preferably does not contain a carbonyl group.

[1127] As the above alkyl group of R 11c , the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, it may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but it is preferably not substituted by any functional group.

[1128] As the above monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 103c (In the formula, R 103c is an alkyl group) can be mentioned.

[1129] As R11c In the above-mentioned alkyl group, 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, but a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[1130] R 12c is an alkylene group having 0 to 3 carbon atoms. The above-mentioned number of carbon atoms is preferably 1 to 3.

[1131] As R 12c the above-mentioned alkylene group may be linear or branched.

[1132] As R 12c the above-mentioned alkylene group preferably does not contain a carbonyl group. As R 12c , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[1133] As R 12c in the above-mentioned alkylene group, the hydrogen atoms bonded to carbon atoms may be substituted by a functional group, for example, may be substituted by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[1134] As the above-mentioned monovalent organic group containing an ester bond, a group represented by the formula: -O-C(=O)-R 104c (wherein, R 104c is an alkyl group) can be cited.

[1135] As R 12c in the above-mentioned alkylene group, 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, but a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[1136] As R 2c and R 3c , preferably independently are alkylene groups having 1 or more carbon atoms that do not contain a carbonyl group, more preferably alkylene groups having 1 to 3 carbon atoms that do not contain a carbonyl group, and further preferably ethylene (-C2H4-) or propylene (-C3H6-).

[1137] As the above-mentioned surfactant (c), the following surfactants can be exemplified. In each formula, A c is as described above.

[1138] [Chemical formula 70]

[1139]

[1140] [Chemical formula 71]

[1141]

[1142] [Chemical formula 72]

[1143]

[1144] [Chemical formula 73]

[1145]

[1146] [Chemical formula 74]

[1147]

[1148] [Chemical formula 75]

[1149]

[1150] [Chemical formula 76]

[1151]

[1152] [Chemical formula 77]

[1153]

[1154] The surfactant (c) is a new compound and can be produced, for example, by the production methods exemplified below.

[1155] The surfactant (c) can be suitably produced by a production method including step (11c), step (12c), step (13c), and step (14c), wherein

[1156] Step (11c) is to react a compound (10c) represented by the formula:

[1157] [Chemical formula 78]

[1158]

[1159] (wherein R 3c As described above, E c is a leaving group) with lithium and a chlorosilane compound represented by the formula: R 201c 3Si-Cl (wherein R 201c is independently an alkyl group or an aryl group) to obtain a compound (11c) represented by the formula:

[1160] [Chemical formula 79]

[1161]

[1162] (wherein R 3c , R 201c and E c are as described above) of the step,

[1163] Step (12c) involves reacting compound (11c) with an alkene represented by the formula:

[1164] [Chemical Formula 80]

[1165]

[1166] (wherein R 1c As described above, R 21c is a single bond or a divalent linking group) to obtain a compound represented by the formula:

[1167] [Chemical Formula 81]

[1168]

[1169] (wherein R 1c , R 21c , R 3c and E c are as described above) of compound (12c).

[1170] Step (13c) involves detaching the leaving group of compound (12c) to obtain a compound represented by the formula:

[1171] [Chemical Formula 82]

[1172]

[1173] (wherein R 1c , R 21c and R 3c are as described above) of compound (13c).

[1174] Step (14c) involves oxidizing compound (13c) to obtain a compound represented by the formula:

[1175] [Chemical Formula 83]

[1176]

[1177] (wherein R 1c , R 21c and R 3c are as described above) of compound (14c).

[1178] When R 1c contains a furan ring, for example, the furan ring can be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[1179] In step (11c), it is preferred that lithium and the above-mentioned chlorosilane compound react in advance to obtain a lithium silyloxide compound, and then the lithium silyloxide compound reacts with compound (10c) to obtain compound (11c).

[1180] E c represents a leaving group. Examples of the leaving group include tert-butyldimethylsilyl (TBS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), benzyl (Bn), etc.

[1181] As R 21c , a single bond or a linear or branched alkylene group having 1 or more carbon atoms is preferred.

[1182] Examples of the chlorosilane compound include

[1183] [Chemical formula 84]

[1184]

[1185] Any of the reactions in step (11c) can be carried out in a solvent. As the solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred. Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ethers (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[1186] As the temperature of the reaction between lithium and the above-mentioned chlorosilane compound in step (11c), -78°C to 100°C is preferred, and 10°C to 40°C is more preferred.

[1187] As the temperature of the reaction between the lithium silyloxide compound and compound (10c) in step (11c), -100°C to 0°C is preferred, and -80°C to -50°C is more preferred.

[1188] As the pressure of the reaction between lithium and the above-mentioned chlorosilane compound in step (11c), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[1189] As the pressure of the reaction between the lithium silyloxide compound and compound (10c) in step (11c), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[1190] As the reaction time of lithium and the above-mentioned chlorosilane compound in step (11c), it is preferably 0.1 hour to 72 hours, more preferably 6 hours to 10 hours.

[1191] As the reaction time of the above-mentioned lithium silyloxy compound and compound (10c) in step (11c), it is preferably 0.1 hour to 72 hours, more preferably 1 hour to 2 hours.

[1192] In step (12c), as the reaction ratio of compound (11c) and the above-mentioned olefin, considering the improvement of yield and the reduction of waste, relative to 1 mole of compound (11c), the above-mentioned olefin is preferably 1 mole to 2 moles, more preferably 1 mole to 1.1 moles.

[1193] The reaction in step (12c) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[1194] Examples of the above-mentioned thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide, 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride, etc.

[1195] Examples of the above-mentioned base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, etc.

[1196] As the above-mentioned solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an alcohol or an ether is further preferred.

[1197] Examples of the above-mentioned alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[1198] Examples of the above-mentioned ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc., among which tetrahydrofuran and diethyl ether are preferred.

[1199] As the reaction temperature in step (12c), it is preferably 40°C to 60°C, more preferably 50°C to 55°C.

[1200] As the reaction pressure in step (12c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1201] As the reaction time in step (12c), it is preferably 0.1 hour to 72 hours, more preferably 6 hours to 10 hours.

[1202] The elimination reaction of the leaving group in step (13c) can be carried out by using fluoride ions or an acid. As methods for eliminating the leaving group, for example, the following can be cited: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF; a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), or ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[1203] The elimination reaction of the leaving group in step (13c) can be carried out in a polar solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[1204] As the above ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ethers (15-crown-5, 18-crown-6), etc. can be cited, and among them, tetrahydrofuran and diethyl ether are preferred.

[1205] As the temperature of the reaction in step (13c), 0 to 40 °C is preferred, and 0 to 20 °C is more preferred.

[1206] As the pressure of the reaction in step (13c), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[1207] As the reaction time in step (13c), 0.1 hour to 72 hours is preferred, and 3 hours to 8 hours is more preferred.

[1208] The oxidation in step (14c) can be carried out in a solvent in the presence of sodium chlorite.

[1209] As the above solvent, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, etc. and water can be used. As the buffer solution, a disodium hydrogen phosphate solution can be used.

[1210] Compound (14c) can be contacted with a base to convert -COOH into a salt form. As the above base, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. can be cited, and an aqueous solution of ammonia is preferably used.

[1211] After each step is completed, the solvent can be removed by distillation or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[1212] Surfactant (c) can also be suitably manufactured by a manufacturing method including step (21c), step (22c), and step (23c), wherein

[1213] Step (21c) is to make the formula:

[1214] [Chemical Formula 85]

[1215]

[1216] (In the formula, R 3c As described above, R 22c is a monovalent organic group, and E c is a leaving group) The ketone shown reacts with the carboxylic acid ester of the formula:

[1217] [Chemical Formula 86]

[1218]

[1219] (In the formula, R 1c As described above, R 23c is a monovalent organic group) to obtain a compound of the formula:

[1220] [Chemical Formula 87]

[1221]

[1222] (In the formula, R 1c , R 3c and E c As described above, R 24c is a single bond or a divalent linking group) The step of the compound (21c) shown,

[1223] Step (22c) is to remove the leaving group possessed by the compound (21c) to obtain a compound of the formula:

[1224] [Chemical Formula 88]

[1225]

[1226] (In the formula, R 1c , R 24c and R 3c As described above) The step of the compound (22c) shown,

[1227] Step (23c) is to oxidize the compound (22c) to obtain a compound of the formula:

[1228] [Chemical Formula 89]

[1229]

[1230] (In the formula, R 1c , R 24c and R 3c As described above) The step of the compound (23c) shown.

[1231] R 1cIn the case of containing a furan ring, for example, the furan ring can be ring-opened with an acid to be converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[1232] E c represents a leaving group. Examples of the above-mentioned leaving group include tert-butyldimethylsilyl (TBS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), benzyl (Bn), etc.

[1233] As R 22c , a linear or branched alkyl group having 1 or more carbon atoms is preferred, and methyl is more preferred.

[1234] As R 23c , a linear or branched alkyl group having 1 or more carbon atoms is preferred, and methyl is more preferred.

[1235] As R 24c , a linear or branched alkylene group having 1 or more carbon atoms is preferred, and methylene (-CH2-) is more preferred.

[1236] The reaction in step (21c) can be carried out in a solvent in the presence of a base.

[1237] Examples of the above base include sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, etc.

[1238] As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and alcohol and ether are further preferred.

[1239] Examples of the above alcohol include methanol, ethanol, 1-propanol, isopropanol, etc.

[1240] Examples of the above ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), etc., and tetrahydrofuran and diethyl ether are preferred.

[1241] As the temperature of the reaction in step (21c), 0 to 40 °C is preferred, and 0 to 20 °C is more preferred.

[1242] As the pressure of the reaction in step (21c), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[1243] As the reaction time in step (21c), 0.1 hour to 72 hours is preferred, and 3 hours to 8 hours is more preferred.

[1244] The elimination reaction of the leaving group in step (22c) can be carried out by using fluoride ions or an acid. As methods for eliminating the leaving group, for example, there can be mentioned: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF; a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), or ammonium fluoride; and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[1245] The elimination reaction of the leaving group in step (22c) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[1246] As the above ether, there can be mentioned ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), crown ethers (15-crown-5, 18-crown-6), etc. Among them, tetrahydrofuran and diethyl ether are preferred.

[1247] As the temperature of the reaction in step (22c), 0 to 40 °C is preferred, and 0 to 20 °C is more preferred.

[1248] As the pressure of the reaction in step (22c), 0.1 MPa to 5 MPa is preferred, and 0.1 MPa to 1 MPa is more preferred.

[1249] As the reaction time in step (22c), 0.1 hour to 72 hours is preferred, and 3 hours to 8 hours is more preferred.

[1250] The oxidation in step (23c) can be carried out in a solvent in the presence of sodium chlorite.

[1251] As the above solvent, an alcohol and water can be used. As the buffer solution, a disodium hydrogen phosphate solution can be used.

[1252] The compound (23c) can be brought into contact with a base to convert -COOH into a salt form. As the above base, there can be mentioned sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. An aqueous solution of ammonia is preferably used.

[1253] After each step is completed, the solvent can be removed by distillation or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[1254] Surfactant (c) can also be suitably produced by a production method including step (31c), step (32c), step (33c), and step (34c), wherein,

[1255] Step (31c) is to make the formula: Y c -R3c -CH2-OE c

[1256] (wherein, R 3c As described above, Y c is a halogen atom, and E c is a leaving group) of the haloalkyl represented by the formula:

[1257] [Chemical formula 90]

[1258]

[1259] (wherein, R 1c As described above) reacts with lithium acetylide represented by the formula:

[1260] [Chemical formula 91]

[1261]

[1262] (wherein, R 1c , R 3c and E c As described above) to obtain the compound (31c) of the formula:

[1263] Step (32c) is to oxidize the compound (31c) to obtain the formula

[1264] [Chemical formula 92]

[1265]

[1266] (wherein, R 1c , R 3c and E c As described above) to obtain the compound (32c) of the formula:

[1267] Step (33c) is to remove the leaving group of the compound (32c) to obtain the formula:

[1268] [Chemical formula 93]

[1269]

[1270] (wherein, R 1c and R 3c As described above) to obtain the compound (33c) of the formula:

[1271] Step (34c) is to oxidize the compound (33c) to obtain the formula:

[1272] [Chemical formula 94]

[1273]

[1274] (wherein, R1c and R 3c The process of the compound (34c) as described above).

[1275] R 1c In the case where a furan ring is included, for example, the furan ring can be ring-opened with an acid to be converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred among them.

[1276] E c represents a leaving group. Examples of the above-mentioned leaving group include tert-butyldimethylsilyl (TBS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), benzyl (Bn), etc.

[1277] In step (31c), as the reaction ratio of the above-mentioned haloalkyl to the above-mentioned lithium acetylide, considering the improvement of the yield and the reduction of waste, relative to 1 mole of the above-mentioned haloalkyl, the above-mentioned lithium acetylide is preferably 1 mole to 2 moles, more preferably 1 mole to 1.2 moles.

[1278] The reaction in step (31c) can be carried out in a solvent. As the above-mentioned solvent, hexane is preferred.

[1279] The temperature of the reaction in step (31c) is preferably -100°C to -40°C, more preferably -80°C to -50°C.

[1280] The pressure of the reaction in step (31c) is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1281] The reaction time in step (31c) is preferably 0.1 hour to 72 hours, more preferably 6 hours to 10 hours.

[1282] The oxidation in step (32c) can be carried out as follows: After treating [(Cn * )Ru III (CF3CO2)3]·H2O (wherein Cn * represents 1,4,7-trimethyl-1,4,7-triazabicyclononane) with (NH4)2Ce(NO3)6 and trifluoroacetic acid, a complex is formed by adding sodium perchlorate, and this complex is used to carry out the oxidation in a nitrile-based solvent.

[1283] After the oxidation is terminated, it can be neutralized with a base, and the compound (32c) is extracted with an organic solvent such as ether.

[1284] As the temperature of the reaction in step (32c), it is preferably 30°C to 100°C, more preferably 40°C to 90°C.

[1285] As the pressure of the reaction in step (32c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1286] As the reaction time in step (32c), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 8 hours.

[1287] The elimination reaction of the leaving group in step (33c) can be carried out by using fluoride ions or an acid. As the method for eliminating the leaving group, for example, there can be mentioned: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF; a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium tetrafluoroborate (LiBF4), or ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[1288] The elimination reaction of the leaving group in step (33c) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, a non-protic polar solvent is more preferred, and an ether is further preferred.

[1289] As the above ether, ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraethylene glycol dimethyl ether (tetraglyme), crown ethers (15-crown-5, 18-crown-6), etc. can be mentioned. Among them, tetrahydrofuran and diethyl ether are preferred.

[1290] As the reaction temperature in step (33c), it is preferably 0 to 40 °C, more preferably 0 to 20 °C.

[1291] As the reaction pressure in step (33c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1292] As the reaction time in step (33c), it is preferably 0.1 hour to 72 hours, more preferably 3 hours to 8 hours.

[1293] The oxidation in step (34c) can be carried out in a solvent in the presence of sodium chlorite.

[1294] As the above solvent, an alcohol and water can be used. As the buffer solution, a disodium hydrogen phosphate solution can be used.

[1295] Compound (34c) can be contacted with a base to convert -COOH into a salt form. As the above base, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. can be mentioned. An aqueous solution of ammonia is preferably used.

[1296] After each step is completed, the solvent can be removed by distillation or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[1297] The surfactant (c) can also be suitably produced by a production method including step (51c), step (52c), step (53c), and step (54c), where

[1298] Step (51c) is to react divinyl ketone represented by the formula:

[1299] [Chemical formula 95]

[1300]

[1301] with 2-methylfuran represented by the formula:

[1302] [Chemical formula 96]

[1303]

[1304] to obtain a compound (51c) represented by the formula:

[1305] [Chemical formula 97]

[1306]

[1307] The step of

[1308] Step (52c) is to react the compound (51c) with furan represented by the formula:

[1309] [Chemical formula 98]

[1310]

[1311] to obtain a compound (52c) represented by the formula:

[1312] [Chemical formula 99]

[1313]

[1314] The step of

[1315] Step (53c) is to heat the compound (52c) in the presence of an acid to thereby obtain a compound (53c) represented by the formula:

[1316] [Chemical formula 100]

[1317]

[1318] The step of

[1319] Step (54c) is to oxidize the compound (53c) to obtain a compound represented by the formula:

[1320] [Chemical 101]

[1321]

[1322] Process for the compound (54c) shown.

[1323] In step (51c), as the reaction ratio of divinyl ketone to 2-methylfuran, considering the improvement of yield and the reduction of waste, relative to 1 mole of divinyl ketone, 2-methylfuran is preferably 0.5 to 1 mole, more preferably 0.6 to 0.9 mole.

[1324] The reaction in step (51c) is preferably carried out in the presence of an acid. Examples of the above acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[1325] Regarding the amount of the above acid in step (51c), considering the improvement of yield and the reduction of waste, relative to 1 mole of divinyl ketone, it is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole.

[1326] The reaction in step (51c) can be carried out in a polar solvent. Examples of the above solvent include water and acetonitrile.

[1327] As the reaction temperature in step (51c), it is preferably 20°C to 100°C, more preferably 40°C to 100°C.

[1328] As the reaction pressure in step (51c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1329] As the reaction time in step (51c), it is preferably 0.1 hour to 72 hours, more preferably 4 hours to 8 hours.

[1330] In step (52c), as the reaction ratio of compound (51c) to furan, considering the improvement of yield and the reduction of waste, relative to 1 mole of compound (51c), furan is preferably 1 to 2 moles, more preferably 1 to 1.1 moles.

[1331] The reaction in step (52c) is preferably carried out in the presence of an acid. Examples of the above acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[1332] Regarding the amount of the above acid in step (52c), considering the improvement of yield and the reduction of waste, relative to 1 mole of compound (51c), it is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole.

[1333] The reaction in step (52c) can be carried out in a polar solvent. Examples of the above solvent include water.

[1334] As the temperature of the reaction in step (52c), it is preferably 20°C to 100°C, more preferably 40°C to 100°C.

[1335] As the pressure of the reaction in step (52c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1336] As the reaction time in step (52c), it is preferably 0.1 hour to 72 hours, more preferably 4 hours to 8 hours.

[1337] In step (53c), the furan ring is opened by heating compound (52c) in the presence of an acid.

[1338] As the above-mentioned acid, hydrochloric acid and sulfuric acid are preferred.

[1339] The reaction in step (53c) can be carried out in a polar solvent. As the above-mentioned solvent, water is preferred.

[1340] As the temperature of the reaction in step (53c), it is preferably 50°C to 100°C, more preferably 70°C to 100°C.

[1341] As the pressure of the reaction in step (53c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1342] As the reaction time in step (53c), it is preferably 0.1 hour to 72 hours, more preferably 1 hour to 12 hours.

[1343] The oxidation in step (54c) can be carried out in a solvent in the presence of sodium chlorite.

[1344] As the above-mentioned solvent, tert-butanol and water can be used. As the buffer solution, disodium hydrogen phosphate solution can be used.

[1345] Compound (54c) can be contacted with a base to convert -COOH into a salt form. As the above-mentioned base, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. can be mentioned, and an aqueous solution of ammonia is preferably used.

[1346] After each step is completed, the solvent can be removed by distillation or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[1347] Surfactant (c) can also be suitably produced by a production method including step (61c) and step (62c), wherein

[1348] Step (61c) is to make the formula:

[1349] [Chemical formula 102]

[1350]

[1351] (wherein, R 1c As described above, R 21c is a single bond or a divalent linking group) and an alkyne represented by the formula:

[1352] [Chemical formula 103]

[1353]

[1354] (wherein, Y 61c is an alkyl ester group) to obtain a compound represented by the formula:

[1355] [Chemical formula 104]

[1356]

[1357] (wherein, R 1c , R 21c and Y 61c are as described above) (61c),

[1358] Step (62c) is to allow a base to act on compound (61c) and then allow an acid to act to obtain a compound represented by the formula:

[1359] [Chemical formula 105]

[1360]

[1361] (wherein, R 1c and R 21c are as described above) (62c).

[1362] When R 1c contains a furan ring, for example, the furan ring can be opened with an acid to be converted into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, p-toluenesulfonic acid, etc., and acetic acid is preferred.

[1363] As R 21c , a single bond or a linear or branched alkylene having 1 or more carbon atoms is preferred.

[1364] In step (61c), as the reaction ratio of the above-mentioned alkene to the above-mentioned alkyne, in consideration of improving the yield and reducing waste, relative to 1 mole of the above-mentioned alkyne, the above-mentioned alkene is preferably 0.5 mole to 2 moles, more preferably 0.6 mole to 1.2 moles.

[1365] The reaction in step (61c) is preferably carried out in the presence of a metal catalyst. Examples of the above-mentioned metal include ruthenium, etc.

[1366] Regarding the amount of the above-mentioned metal catalyst in step (61c), in consideration of the improvement of the yield and the reduction of waste, it is preferably 0.01 mol to 0.4 mol, more preferably 0.05 mol to 0.1 mol, relative to 1 mol of the above-mentioned olefin.

[1367] The reaction in step (61c) can be carried out in a polar solvent. As the above-mentioned solvent, water, acetonitrile, dimethylacetamide, and dimethylformamide are preferred.

[1368] As the temperature of the reaction in step (61c), it is preferably 20°C to 160°C, more preferably 40°C to 140°C.

[1369] As the pressure of the reaction in step (61c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1370] As the reaction time in step (61c), it is preferably 0.1 hour to 72 hours, more preferably 4 hours to 8 hours.

[1371] In step (62c), as the reaction ratio of compound (61c) to the above-mentioned base, in consideration of the improvement of the yield and the reduction of waste, the above-mentioned base is preferably 0.6 mol to 2 mol, more preferably 0.8 mol to 1.1 mol, relative to 1 mol of compound (61c).

[1372] Regarding the amount of the above-mentioned acid in step (62c), in consideration of the improvement of the yield and the reduction of waste, it is preferably 1.0 mol to 20.0 mol, more preferably 1.0 mol to 10.0 mol, relative to 1 mol of compound (61c).

[1373] The reaction in step (62c) can be carried out in a polar solvent. As the above-mentioned solvent, water is preferred.

[1374] As the temperature of the reaction in step (62c), it is preferably 0 to 100°C, more preferably 20°C to 100°C.

[1375] As the pressure of the reaction in step (62c), it is preferably 0.1 MPa to 5 MPa, more preferably 0.1 MPa to 1 MPa.

[1376] As the reaction time in step (62c), it is preferably 0.1 hour to 72 hours, more preferably 4 hours to 8 hours.

[1377] Compound (62c) can be contacted with a base to convert -COOH into a salt form. As the above-mentioned base, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. can be mentioned, and an aqueous solution of ammonia is preferably used.

[1378] After each step is terminated, the solvent can be removed by distillation or distillation, purification, etc. can be carried out to improve the purity of the obtained compound.

[1379] The surfactant (d) will be described.

[1380] In formula (d), R 1d 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.

[1381] When the number of carbon atoms of the above alkyl group is 3 or more, it may contain a monovalent or divalent heterocycle and may form a ring. As the above heterocycle, an unsaturated heterocycle is preferred, and an oxygen-containing unsaturated heterocycle is more preferred. For example, a furan ring can be cited. R 1d In, the divalent heterocycle can be inserted between 2 carbon atoms, the divalent heterocycle can also be located at the end and bonded to -C(=O)-, and the monovalent heterocycle can be located at the end of the above alkyl group.

[1382] It should be noted that in this specification, the "number of carbon atoms" of the above alkyl group also includes the number of carbon atoms constituting the above heterocycle.

[1383] Regarding the above substituents that the above alkyl group as R 1d can have, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a hydroxyl group are preferred, and methyl and ethyl are particularly preferred.

[1384] As R 1d the above alkyl group preferably does not contain a carbonyl group.

[1385] In the above alkyl group, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[1386] The above alkyl group preferably does not have any substituents.

[1387] As R 1d , a linear or branched alkyl group having 1 to 10 carbon atoms with or without substituents or a cyclic alkyl group having 3 to 10 carbon atoms with or without substituents is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms without substituents is further preferred, a linear or branched alkyl group having 1 to 3 carbon atoms without substituents is still more preferred, methyl (-CH3) or ethyl (-C2H5) is particularly preferred, and methyl (-CH3) is most preferred.

[1388] In formula (d), R 2d and R 4d are independently H or a substituent. Two or more R 2d and R 4d can be the same or different, respectively.

[1389] Regarding the above-mentioned substituents as R 2d and R 4d preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a hydroxyl group, particularly preferably a methyl group or an ethyl group.

[1390] As R 2d and R 4d the above-mentioned alkyl groups preferably do not contain a carbonyl group. In the above-mentioned alkyl groups, 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but preferably a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[1391] The above-mentioned alkyl groups preferably do not have any substituents.

[1392] Regarding the above-mentioned alkyl groups as R 2d and R 4d preferably a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group, further preferably a linear or branched alkyl group having 1 to 3 carbon atoms without substituents, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[1393] As R 2d and R 4d , preferably independently H or a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group, more preferably H or a linear or branched alkyl group having 1 to 3 carbon atoms without substituents, still more preferably H, a methyl group (-CH3) or an ethyl group (-C2H5), particularly preferably H.

[1394] In formula (d), R 3d is an alkylene group having 1 to 10 carbon atoms with or without substituents. When there are two or more R 3d , they can be the same or different.

[1395] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[1396] In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[1397] The above-mentioned alkylene group preferably has no substituent.

[1398] As the above-mentioned alkylene group, preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted or a cyclic alkylene group having 3 to 10 carbon atoms which may be substituted or not, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group, further preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[1399] R 1d , R 2d , R 3d and R 4d Any two of them can be bonded to each other to form a ring.

[1400] In formula (d), n is an integer of 1 or more. As n, an integer of 1-40 is preferable, an integer of 1-30 is more preferable, and an integer of 5-25 is further preferable.

[1401] In formula (d), p and q are independently an integer greater than or equal to 0. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[1402] The total of n, p and q is preferably an integer of 6 or more. The total of n, p and q is more preferably an integer of 8 or more. The total of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and further preferably an integer of 40 or less.

[1403] In formula (d), A d -SO3X d or -COOX d (X d H, metal atoms, NR 5d 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5d is H or an organic group, which may be the same or different). 5d The organic group in is preferably an alkyl group. 5d, preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms. As the above-mentioned metal atom, a monovalent or divalent metal atom can be mentioned, and an alkali metal (Group 1), an alkaline earth metal (Group 2), etc. can be mentioned, and Na, K or Li is preferred. X d may be a metal atom or NR 5d 4 (R 5d as described above).

[1404] As X d , preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5d 4. For the reason of being easily soluble in water, more preferably H, Na, K, Li or NH4, and for the reason of being more easily soluble in water, still more preferably Na, K or NH4, particularly preferably Na or NH4, and for the reason of being easily removed, most preferably NH4. When X d is NH4, the above-mentioned surfactant has excellent solubility in an aqueous medium and is not likely to leave a metal component in PTFE or the final product.

[1405] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding the carbonyl group included in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without substituents, and R 6d is H or an alkyl group having 1 to 4 carbon atoms with or without substituents. The number of carbon atoms of the above-mentioned alkylene group is more preferably 1 to 5. In addition, the above-mentioned R 6d is more preferably H or methyl. * refers to the side bonded to A d in the formula.

[1406] L is preferably a single bond.

[1407] The above-mentioned surfactant preferably has an integrated value of the intensities of all peaks observed in the region of chemical shift 2.0 ppm to 5.0 ppm in the 1 H-NMR spectrum of 10 or more.

[1408] The above-mentioned surfactant preferably has an integrated value of the intensities of all peaks observed in the region of chemical shift 2.0 ppm to 5.0 ppm in the 1 H-NMR spectrum within the above range. In this case, the above-mentioned surfactant preferably has a ketone structure in the molecule.

[1409] Among the above surfactants, the above integral value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and still more preferably 70 or less.

[1410] The above integral value is measured at room temperature using a heavy water solvent. The heavy water is 4.79 ppm.

[1411] Examples of the above surfactant (d) include, for example,

[1412] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK,

[1413] CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa,

[1414] CH3C(O)CH2CH2CH2CH2CH2CH2COONa,

[1415] CH3C(O)CH2CH2CH2CH2CH2COONa,

[1416] CH3C(O)CH2CH2CH2CH2COONa,

[1417] CH3C(O)CH2CH2CH2COONa,

[1418] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[1419] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[1420] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[1421] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[1422] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa,

[1423] CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa,

[1424] CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa,

[1425] CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa,

[1426] CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa,

[1427] CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa,

[1428] CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa,

[1429] CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa,

[1430] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa,

[1431] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK,

[1432] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK,

[1433] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa,

[1434] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa,

[1435] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa,

[1436] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH,

[1437] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi,

[1438] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4,

[1439] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa,

[1440] CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK,

[1441] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1442] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1443] CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1444] CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na,

[1445] CH3C(O)CH2CH2CH2CH2CH2SO3Na,

[1446] CH3C(O)CH2CH2CH2CH2SO3Na,

[1447] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1448] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1449] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1450] (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1451] (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1452] (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1453] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1454] CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na,

[1455] CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na,

[1456] CH3C(O)CH2CH2CH2CH2CH2SO3Na,

[1457] CH3C(O)CH2CH2CH2CH2SO3Na,

[1458] CH3C(O)CH2CH2CH2SO3Na,

[1459] CH3C(O)CH2CH2SO3Na,

[1460] CH3C(O)CH2SO3Na,

[1461] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na,

[1462] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na,

[1463] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na,

[1464] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na,

[1465] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na,

[1466] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na,

[1467] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H,

[1468] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K,

[1469] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li,

[1470] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4,

[1471] CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na, etc.

[1472] The surfactant (d) is a new compound and can be produced, for example, by the production methods exemplified below.

[1473] The surfactant (d) can be suitably produced by a production method including step (11d), where

[1474] Step (11d) is to react the compound (10d) represented by the following formula:

[1475] [Chemical formula 106]

[1476]

[1477] (In the formula, R 1d , R 2d and n are as described above)

[1478] shown with the sultone represented by the following formula:

[1479] [Chemical formula 107]

[1480]

[1481] (In the formula, R 3d is as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding the carbonyl groups included in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group with 1 to 10 carbon atoms which may or may not have substituents, R 6d is H or an alkyl group with 1 to 4 carbon atoms which may or may not have substituents. * refers to the side bonded to -S(=O)2- in the formula) to obtain the following formula:

[1482] [Chemical formula 108]

[1483]

[1484] (In the formula, R 1d to R 3d , n and X d are as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6dCO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d the carbonyl group contained in CO-B-), B is a single bond or an alkylene group with 1 to 10 carbon atoms with or without substituents, R 6d is H or an alkyl group with 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to -OSO3X in the formula d the step of the compound (11d) shown).

[1485] The reaction in step (11d) can be carried out in the presence of a base.

[1486] Examples of the above base include sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, etc. Relative to 1 mole of the compound (10d), the above base can be used in an amount of 0.5 mole to 20 moles.

[1487] The reaction in step (11d) can be carried out in a solvent.

[1488] As the above solvent, an organic solvent is preferred, and a non-protic polar solvent is more preferred. Examples of the above organic solvent include ethers, aromatic compounds, nitriles, halogenated hydrocarbons, etc.

[1489] Examples of the above ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and diethyl ether and tetrahydrofuran are preferred among them.

[1490] Examples of the above aromatic compound include benzene, toluene, xylene, etc., and benzene is preferred among them.

[1491] Examples of the above nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and acetonitrile is preferred among them.

[1492] Examples of the above halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and dichloromethane and chloroform are preferred among them.

[1493] As the temperature of the reaction in step (11d), -78°C to 150°C is preferred, and -20°C to 100°C is more preferred.

[1494] As the pressure of the reaction in step (11d), 0 to 10 MPa is preferred, and 0 to 1.0 MPa is more preferred.

[1495] As the reaction time in step (11d), 0.1 hour to 72 hours is preferred, and 0.1 hour to 48 hours is more preferred.

[1496] The surfactant (d) can also be suitably produced by a production method including step (21d), wherein

[1497] Step (21d) is to use the following formula:

[1498] [Chemical formula 109]

[1499]

[1500] (wherein, R 1d ~R 4d , n, p and q are as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding the carbonyl groups included in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group with 1 to 10 carbon atoms with or without substituents, and R 6d is H or an alkyl group with 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to -CH2-OH in the formula)

[1501] oxidize the compound (20d) shown to obtain the following formula:

[1502] [Chemical formula 110]

[1503]

[1504] (wherein, R 1d ~R 4d , n, p, q and X d are as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding the carbonyl groups included in -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group with 1 to 10 carbon atoms with or without substituents, and R 6d is H or an alkyl group with 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to -CH2-COOX d in the formula)

[1505] The step of the compound (21d) shown.

[1506] The oxidation in step (21d) can be carried out by allowing a nitrosating agent to act on the compound (20d).

[1507] As the above-mentioned nitrosating agent, sodium nitrite, nitrosyl sulfuric acid, isoamyl nitrite, etc. can be used.

[1508] Relative to 1 mole of the compound (20d), the above-mentioned nitrosating agent can be used in an amount of 0.5 mole to 10 moles.

[1509] The oxidation in the step (21d) can be carried out in a solvent. As the above-mentioned solvent, trifluoroacetic acid, acetonitrile, etc. can be used.

[1510] As the temperature of the oxidation in the step (21d), -78°C to 200°C is preferred, and -20°C to 100°C is more preferred.

[1511] As the pressure of the oxidation in the step (21d), 0 to 10 MPa is preferred, and 0 to 1.0 MPa is more preferred.

[1512] As the time of the oxidation in the step (21d), 0.1 hour to 72 hours is preferred, and 0.1 hour to 24 hours is more preferred.

[1513] The compound (10d) and the compound (20d) can be produced by a production method including the step (101d) and the step (102d), wherein

[1514] The step (101d) is to use the following formula:

[1515] R 11d -CH=CH-Y 1d -OH

[1516] (In the formula, R 11d is H, 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. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. Y 1d is -(CR 2d 2) n - or -(CR 2d 2)n-(OR 3d ) p -(CR 4d 2) q -L-CH2-(R 2d ~R 4d , n, L, p and q are as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR6d (The carbonyl group contained in CO-B-), B is a single bond or an alkylene group with 1 to 10 carbon atoms with or without substituents, R 6d is H or an alkyl group with 1 to 4 carbon atoms with or without substituents. * refers to the side bonded to the -CH2- bond in the formula)) The compound (100d) shown is hydroxylated to obtain the following formula:

[1517] [Chemical formula 111]

[1518]

[1519] (In the formula, R 11d and Y 1d are as described above) The step of the compound (101d) shown

[1520] Step (102d) is to oxidize the compound (101d) to obtain the following formula:

[1521] [Chemical formula 112]

[1522]

[1523] (In the formula, R 11d and Y 1d are as described above) The step of the compound (102d) shown

[1524] As the above alkyl group of R 11d preferably does not contain a carbonyl group.

[1525] Among the above alkyl groups of R 11d , up to 75% of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, up to 50% can be substituted by halogen atoms, up to 25% can be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group without fluorine atoms, chlorine atoms and other halogen atoms.

[1526] The above alkyl group preferably does not have any substituents.

[1527] As R 11d , preferably H, a linear or branched alkyl group with 1 to 9 carbon atoms with or without substituents, or a cyclic alkyl group with 3 to 9 carbon atoms with or without substituents, more preferably H, a linear or branched alkyl group with 1 to 9 carbon atoms without a carbonyl group or a cyclic alkyl group with 3 to 9 carbon atoms without a carbonyl group, further preferably H, or a linear or branched alkyl group with 1 to 9 carbon atoms without substituents, still more preferably H, methyl (-CH3) or ethyl (-C2H5), particularly preferably H or methyl (-CH3), and most preferably H.

[1528] The hydroxylation in step (101d) can be carried out, for example, by the following methods: (1d) a method of reacting iron(II) phthalocyanine (Fe(Pc)) and sodium borohydride with compound (100d) in an oxygen atmosphere; (2d) a method of reacting isopinocampheylborane (IpcBH2) with compound (100d) and then oxidizing the resulting intermediate (dialkylboron).

[1529] In method (1d), the amount of iron(II) phthalocyanine can be a catalytic amount and can be used in an amount of 0.001 mol to 1.2 mol relative to 1 mol of compound (100d).

[1530] In method (1d), sodium borohydride can be used in an amount of 0.5 mol to 20 mol relative to 1 mol of compound (100d).

[1531] The reaction of method (1d) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, nitrogen-containing polar organic compounds, etc.

[1532] As the above ethers, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be mentioned, and among them, diethyl ether and tetrahydrofuran are preferred.

[1533] As the above halogenated hydrocarbons, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be mentioned, and among them, dichloromethane and chloroform are preferred.

[1534] As the above aromatic hydrocarbons, benzene, toluene, xylene, etc. can be mentioned, and among them, benzene and toluene are preferred.

[1535] As the above nitriles, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. can be mentioned, and among them, acetonitrile is preferred.

[1536] As the above nitrogen-containing polar organic compounds, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. can be mentioned, and among them, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[1537] As the temperature of the reaction of method (1d), -78°C to 200°C is preferred, and more preferably 0 to 150°C.

[1538] As the pressure of the reaction of method (1d), 0 to 5.0 MPa is preferred, and more preferably 0.1 MPa to 1.0 MPa.

[1539] As the reaction time of method (1d), 0.1 hour to 72 hours is preferred, and more preferably 0.1 hour to 48 hours.

[1540] In method (2d), per 1 mole of compound (100d), isopinocampheyl borane can be used in an amount of 1.0 mole to 10.0 moles.

[1541] The reaction of compound (100d) with isopinocampheyl borane can be carried out in a solvent. As the above-mentioned solvent, an organic solvent is preferred, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[1542] As the above-mentioned ether, examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and among them, diethyl ether and tetrahydrofuran are preferred.

[1543] As the above-mentioned halogenated hydrocarbon, examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and among them, dichloromethane and chloroform are preferred.

[1544] As the above-mentioned aromatic hydrocarbon, examples include benzene, toluene, xylene, etc., and among them, benzene and toluene are preferred.

[1545] As the temperature of the reaction of compound (100d) with isopinocampheyl borane, -78°C to 200°C is preferred, and more preferably 0 to 150°C.

[1546] As the pressure of the reaction of compound (100d) with isopinocampheyl borane, 0 to 5.0 MPa is preferred, and more preferably 0.1 MPa to 1.0 MPa.

[1547] As the reaction time of compound (100d) with isopinocampheyl borane, 0.1 hour to 72 hours is preferred, and more preferably 0.1 hour to 48 hours.

[1548] The oxidation in method (2d) can be carried out by allowing an oxidizing agent to act on the above intermediate. As the above-mentioned oxidizing agent, hydrogen peroxide can be cited. Per 1 mole of the above intermediate, the above oxidizing agent can be used in an amount of 0.7 mole to 10 moles.

[1549] The oxidation in method (2d) can be carried out in a solvent. As the above-mentioned solvent, water, methanol, ethanol, etc. can be cited, and among them, water is preferred.

[1550] As the temperature of the oxidation in method (2d), 0 to 100°C is preferred, and more preferably 0 to 80°C.

[1551] As the pressure of the oxidation in method (2d), 0 to 5.0 MPa is preferred, and more preferably 0.1 MPa to 1.0 MPa.

[1552] As the time of the oxidation in method (2d), 0.1 hour to 72 hours is preferred, and more preferably 0.1 hour to 48 hours.

[1553] In step (102d), as a method for oxidizing compound (101d), for example, the following methods can be mentioned: (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation); (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method in which a bleaching agent (about 5-6% aqueous solution of NaOCl) is allowed to act in the presence of a nickel compound such as NiCl2; (e) a method in which a hydrogen acceptor such as an aldehyde or a ketone is allowed to act in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[1554] The oxidation in step (102d) can be carried out in a solvent. As the above-mentioned solvent, water and organic solvents are preferred, and examples include water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, etc.

[1555] As the above-mentioned ketones, examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc., and acetone is preferred among them.

[1556] As the above-mentioned ethers, examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc., and diethyl ether and tetrahydrofuran are preferred among them.

[1557] As the above-mentioned halogenated hydrocarbons, examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc., and dichloromethane and chloroform are preferred among them.

[1558] As the above-mentioned aromatic hydrocarbons, examples include benzene, toluene, xylene, etc., and benzene and toluene are preferred among them.

[1559] As the above-mentioned nitriles, examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc., and acetonitrile is preferred among them.

[1560] As the temperature of the oxidation in step (102d), -78°C to 200°C is preferred, and it can be appropriately selected according to the method adopted.

[1561] As the pressure of the oxidation in step (102d), 0 to 5.0 MPa is preferred, and it can be appropriately selected according to the method adopted.

[1562] As the time of the oxidation in step (102d), 0.1 hour to 72 hours is preferred, and it can be appropriately selected according to the method adopted.

[1563] Compound (10d) and compound (20d) can also be produced by a production method including step (201d), where

[1564] step (201d) is to convert the following formula:

[1565] [Chemical formula 113]

[1566]

[1567] (In the formula, R 1d and Y 1d are as described above. R 101d is an organic group) The compound (200d) shown is ozonized to obtain the following formula:

[1568] [Chemical formula 114]

[1569]

[1570] (In the formula, R 1d and Y 1d are as described above) The process of the compound (201d) shown.

[1571] As R 101d , an alkyl group having 1 to 20 carbon atoms is preferred. Two Rs 101d can be the same or different.

[1572] The ozonolysis in the process (201d) can be carried out by allowing ozone to act on the compound (200d) and then performing post-treatment with a reducing agent.

[1573] Ozone can be generated by silent discharge in oxygen.

[1574] As the reducing agent used in the above post-treatment, zinc, dimethyl sulfide, thiourea, phosphines, etc. can be mentioned, and phosphines are preferred among them.

[1575] The ozonolysis in the process (201d) can be carried out in a solvent. As the above solvent, water and organic solvents are preferred, and water, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc. can be mentioned.

[1576] As the above alcohol, methanol, ethanol, 1-propanol, isopropanol, etc. can be mentioned. Among them, methanol and ethanol are preferred.

[1577] As the above carboxylic acid, acetic acid, propionic acid, etc. can be mentioned. Among them, acetic acid is preferred.

[1578] As the above ether, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be mentioned, and diethyl ether and tetrahydrofuran are preferred among them.

[1579] As the above halogenated hydrocarbon, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be mentioned, and dichloromethane and chloroform are preferred among them.

[1580] As the above aromatic hydrocarbon, benzene, toluene, xylene, etc. can be mentioned, and benzene and toluene are preferred among them.

[1581] As the temperature for ozone decomposition in step (201d), it is preferably -78°C to 200°C, more preferably 0 to 150°C.

[1582] As the pressure for ozone decomposition in step (201d), it is preferably 0 to 5.0 MPa, more preferably 0.1 MPa to 1.0 MPa.

[1583] As the time for ozone decomposition in step (201d), it is preferably 0.1 hour to 72 hours, more preferably 0.1 hour to 48 hours.

[1584] Compound (10d) and compound (20d) can also be produced by a production method including step (301d), step (302d), and step (303d), where

[1585] Step (301d) is to epoxidize the following formula:

[1586] R 21d -CH=CH-Y 1d -OH

[1587] (In the formula, Y 1d is as described above. R 21d is H, 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. When having 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may form a ring) to obtain the following formula:

[1588] [Chemical formula 115]

[1589]

[1590] (In the formula, R 21d and Y 1d are as described above) to obtain the compound (301d) in step,

[1591] Step (302d) is to react compound (301d) with R 22d 2CuLi (R 22d 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. When having 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may form a ring) to obtain the following formula:

[1592] [Chemical formula 116]

[1593]

[1594] (In the formula, R21d 、R 22d and Y 1d The process of the compound (302d) as described above)

[1595] Process (303d) is to oxidize the compound (302d) to obtain the following formula:

[1596] [Chemical formula 117]

[1597]

[1598] (In the formula, R 21d 、R 22d and Y 1d as described above) The process of the compound (303d).

[1599] As the above-mentioned alkyl group of R 21d preferably does not contain a carbonyl group.

[1600] Among the above-mentioned alkyl groups of R 21d , 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[1601] The above-mentioned alkyl group preferably does not have any substituents.

[1602] As R 21d , preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms with or without substituents, or a cyclic alkyl group having 3 to 8 carbon atoms with or without substituents, more preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group or a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group, further preferably H, or a linear or branched alkyl group having 1 to 8 carbon atoms that does not have substituents, particularly preferably H or methyl (-CH3), and most preferably H.

[1603] As the above-mentioned alkyl group of R 22d preferably does not contain a carbonyl group.

[1604] As the above-mentioned alkyl group of R 22d , 75% or less of the hydrogen atoms bonded to carbon atoms can be substituted by halogen atoms, 50% or less can be substituted by halogen atoms, 25% or less can be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[1605] The above-mentioned alkyl group preferably does not have any substituents.

[1606] As R 22d, preferably a linear or branched alkyl group having 1 to 9 carbon atoms with or without substituents, or a cyclic alkyl group having 3 to 9 carbon atoms with or without substituents, more preferably a linear or branched alkyl group having 1 to 9 carbon atoms without a carbonyl group or a cyclic alkyl group having 3 to 9 carbon atoms without a carbonyl group, further preferably a linear or branched alkyl group having 1 to 9 carbon atoms without substituents, particularly preferably methyl (-CH3) or ethyl (-C2H5), and most preferably methyl (-CH3).

[1607] Two Rs 22d may be the same or different.

[1608] R 21d and R 22d The total number of carbon atoms of

[1609] The epoxidation in step (301d) can be carried out by allowing an epoxidizing agent to act on compound (300d).

[1610] Examples of the above epoxidizing agent include m-chloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, tert-butyl hydroperoxide and other peracids, dimethyldioxirane, methyltrifluoromethyldioxirane, etc. Among them, peracids are preferred, and m-chloroperbenzoic acid is more preferred.

[1611] Relative to 1 mole of compound (300d), the above epoxidizing agent can be used in an amount of 0.5 mole to 10.0 moles.

[1612] The epoxidation in step (301d) can be carried out in a solvent. As the above solvent, an organic solvent is preferred, and examples include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridine, nitrogen-containing polar organic compounds, dimethyl sulfoxide, etc. Among them, dichloromethane is preferred.

[1613] Examples of the above ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. Among them, acetone is preferred.

[1614] Examples of the above ethers include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. Among them, diethyl ether and tetrahydrofuran are preferred.

[1615] Examples of the above halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane and chloroform are preferred.

[1616] Examples of the above aromatic hydrocarbons include benzene, toluene, xylene, etc. Among them, benzene and toluene are preferred.

[1617] As the above-mentioned nitrile, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, etc. can be cited, and among them, acetonitrile is preferred.

[1618] As the above-mentioned nitrogen-containing polar organic compound, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. can be cited, and among them, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone are preferred.

[1619] As the temperature of epoxidation in step (301d), -78°C to 200°C is preferred, and more preferably -40°C to 150°C.

[1620] As the pressure of epoxidation in step (301d), 0 to 5.0 MPa is preferred, and more preferably 0.1 MPa to 1.0 MPa.

[1621] As the time of epoxidation in step (301d), 0.1 hour to 72 hours is preferred, and more preferably 0.1 hour to 48 hours.

[1622] In step (302d), relative to 1 mole of compound (301d), the above-mentioned dialkylcopper lithium can be used in an amount of 0.5 mole to 10.0 moles.

[1623] The reaction of step (302d) can be carried out in a solvent. As the above-mentioned solvent, an organic solvent is preferred, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.

[1624] As the above-mentioned ether, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be cited, and among them, diethyl ether and tetrahydrofuran are preferred.

[1625] As the above-mentioned halogenated hydrocarbon, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc. can be cited, and among them, dichloromethane and chloroform are preferred.

[1626] As the above-mentioned aromatic hydrocarbon, benzene, toluene, xylene, etc. can be cited, and among them, benzene and toluene are preferred.

[1627] As the temperature of the reaction in step (302d), -78°C to 200°C is preferred, and more preferably -40°C to 150°C.

[1628] As the pressure of the reaction in step (302d), 0 to 5.0 MPa is preferred, and more preferably 0.1 MPa to 1.0 MPa.

[1629] As the time of the reaction in step (302d), 0.1 hour to 72 hours is preferred, and more preferably 0.1 hour to 48 hours.

[1630] In step (303d), as a method for oxidizing the compound (302d), for example, the following methods can be cited: (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation); (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method in which a bleaching agent (about 5 to 6% aqueous solution of NaOCl) is allowed to act in the presence of a nickel compound such as NiCl2; (e) a method in which a hydrogen acceptor such as an aldehyde or a ketone is allowed to act in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[1631] The oxidation in step (303d) can be carried out in a solvent. As the above solvent, water and an organic solvent are preferred, and water, a ketone, an alcohol, an ether, a halogenated hydrocarbon, an aromatic hydrocarbon, a nitrile, etc. can be cited.

[1632] As the above ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc. can be cited, and acetone is preferred among them.

[1633] As the above alcohol, methanol, ethanol, 1-propanol, isopropanol, etc. can be cited. Methanol and ethanol are preferred among them.

[1634] As the above ether, diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, etc. can be cited, and diethyl ether and tetrahydrofuran are preferred among them.

[1635] As the above halogenated hydrocarbon, dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, etc...

Claims

1. A method for manufacturing polytetrafluoroethylene, characterized in that, The manufacturing method includes a polymerization step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant to obtain polytetrafluoroethylene, the amount of the hydrocarbon surfactant at the start of polymerization is 60 ppm to 10,000 ppm relative to the aqueous medium, the polymerization step includes a step of performing polymerization under conditions where there is substantially no hydrocarbon surfactant in the form of an organic acid and continuously adding a hydrocarbon surfactant, in the step of continuously adding the hydrocarbon surfactant, when the concentration of polytetrafluoroethylene formed in the aqueous medium is less than 0.6% by mass, the hydrocarbon surfactant is started to be added to the aqueous medium, the addition amount of the hydrocarbon surfactant in the step of continuously adding the hydrocarbon surfactant is 0.01% by mass to 10% by mass relative to 100% by mass of the aqueous medium, the amount of the fluorosurfactant in the polymerization step is 10 ppm or less relative to the aqueous medium, The hydrocarbon-based surfactant in the step of continuously adding the hydrocarbon-based surfactant is an anionic surfactant represented by R Z -L-M. In the formula, R Z 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. When the number of carbon atoms is 3 or more, it contains or does not contain a monovalent or divalent heterocycle; L is -ArSO3 - , -SO3 - , -SO4- or -COO - , M is H, a metal atom, NR 5Z 4, an imidazolium having or not having substituents, a pyridinium having or not having substituents, or a phosphonium having or not having substituents, R 5Z is H or an organic group, -ArSO3 - is an arylsulfonate, the polytetrafluoroethylene contains 99.0% by mass or more of polymerization units based on tetrafluoroethylene and 0.00001% by mass to 1.0% by mass of polymerization units based on the modified monomer.

2. The manufacturing method according to claim 1, further including the following step: adding the modified monomer to the aqueous medium before the start of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0% by mass or less.

3. The manufacturing method according to claim 2, wherein, The amount of the modified monomer added before the start of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0% by mass or less is 0.00001% by mass or more relative to the obtained polytetrafluoroethylene.

4. The manufacturing method according to any one of claims 1 to 3, wherein, In the polymerization process, the number of polytetrafluoroethylene particles is 0.6×10 13 or more per mL.

5. The manufacturing method according to any one of claims 1 to 3, wherein, In the polymerization step, the polymerization temperature is 10°C to 150°C.

6. The manufacturing method according to any one of claims 1 to 3, wherein, The modified monomer includes at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene.

7. The manufacturing method according to any one of claims 1 to 3, wherein The modified monomer includes a modified monomer having a functional group capable of reacting in radical polymerization and a hydrophilic group.

8. The manufacturing method according to claim 7, wherein, The modified monomer having a functional group capable of reacting in radical polymerization and a hydrophilic group is a compound represented by the following formula (4), CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4) Wherein, X i , X j and X k are each independently F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a linking group; Z 1 and Z 2 are each independently H, F or CF3, and k is 0 or 1.

9. The manufacturing method according to any one of claims 1 to 3, wherein, the hydrocarbon surfactant in the step of continuously adding the hydrocarbon surfactant is a carboxylic acid type hydrocarbon surfactant.

10. The manufacturing method according to any one of claims 1 to 3, wherein, The polytetrafluoroethylene has a core-shell structure.

11. The manufacturing method according to any one of claims 1 to 3, wherein, The average primary particle size of the polytetrafluoroethylene is 500 nm or less.

12. The manufacturing method according to any one of claims 1 to 3, wherein, The aspect ratio of the primary particles of the polytetrafluoroethylene is 1.45 or less.

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