Method for producing polytetrafluoroethylene

Abstract

To provide a method capable of producing polytetrafluoroethylene having a small average primary particle size in spite of polymerization using a hydrocarbon surfactant.SOLUTION: There is provided a method for producing polytetrafluoroethylene including polymerizing tetrafluoroethylene and a modifying monomer in an aqueous medium in the presence of a hydrocarbon surfactant to obtain polytetrafluoroethylene, wherein an amount of the hydrocarbon surfactant at the initiation of polymerization is more than 50 ppm based on the aqueous medium, and the polytetrafluoroethylene contains 99.0 mass % or more of a polymerization unit based on tetrafluoroethylene and 1.0 mass % or less of a polymerization unit based on the modifying monomer.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] When polytetrafluoroethylene is produced by emulsion polymerization, fluorine-containing anionic surfactants have been used. Recently, the use of hydrocarbon surfactants instead of fluorine-containing anionic surfactants has been proposed.

[0003] Patent Document 1 describes a method for polymerizing a fluoromonomer in a polymerization reactor to form a dispersion of fluoropolymer particles in an aqueous medium, the method comprising an initial period and a stabilization period after the initial period, the initial period comprising: a step of preparing an initial dispersion of fluoropolymer particles in the aqueous medium in the polymerization reactor, the stabilization period comprising: a step of polymerizing a fluoromonomer in the polymerization reactor and a step of adding a hydrocarbon-containing surfactant to the polymerization reactor, and no fluorine-based surfactant is added during the stabilization period.

[0004] Patent Document 2 describes a method for polymerizing a fluoromonomer in a polymerization reactor to form a dispersion of fluoropolymer particles in an aqueous medium, the method including an initial period including a step of adding to the polymerization reactor: (a) an aqueous medium, (b) a water-soluble hydrocarbon-containing compound, (c) a decomposing agent, (d) a fluoromonomer, and (e) a polymerization initiator, during which no fluorosurfactant is added and the decomposing agent is added before the polymerization initiator.

[0005] Patent Document 3 describes a method for polymerizing a fluoromonomer in a polymerization reactor to form a dispersion of fluoropolymer particles in an aqueous medium, the method comprising the steps of adding an aqueous medium, a polymerization initiator, a fluoromonomer, and a hydrocarbon-containing surfactant to the polymerization reactor, and deactivating the hydrocarbon-containing surfactant. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent Publication No. 9,255,164 [Patent Document 2] U.S. Patent Publication No. 8,563,670 [Patent Document 3] U.S. Patent Publication No. 9,074,025 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present disclosure is to provide a production method that can produce polytetrafluoroethylene by polymerization using a hydrocarbon-based surfactant, and further, that can produce polytetrafluoroethylene having a small average primary particle size despite the polymerization using a hydrocarbon-based surfactant. [Means for solving the problem]

[0008] The present disclosure relates to a method for producing polytetrafluoroethylene, which comprises a polymerization step of obtaining polytetrafluoroethylene by polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant, wherein the amount of the hydrocarbon surfactant at the start of polymerization is more than 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.

[0009] The production method of the present disclosure preferably further comprises the step of adding a modifying monomer to the aqueous medium before the initiation of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0 mass% or less. The amount of the modifying monomer added before the initiation of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0 mass% or less is preferably 0.0001 mass% or more based on the polytetrafluoroethylene obtained.

[0010] In the polymerization process, the number of polytetrafluoroethylene particles is 0.6 × 10 13 It is preferable that the number is more than 1 / mL.

[0011] The polymerization step preferably includes a step of continuously adding a hydrocarbon surfactant. In the step of continuously adding the 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.

[0012] In the polymerization step, the polymerization temperature is preferably 10 to 150°C.

[0013] The modifying monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene.

[0014] The modified monomer preferably includes a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group. The modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group is represented by the following formula (4): CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4) (In the formula, X i , Xj and X k are each independently F, Cl, H, or CF; Y 3 is a hydrophilic group; R a is a linking group; Z 1 and Z 2 are each independently H, F or CF3, and k is 0 or 1).

[0015] The hydrocarbon surfactant is preferably a carboxylic acid type hydrocarbon surfactant.

[0016] The above polymerization step is preferably carried out substantially in the absence of a fluorine-containing surfactant.

[0017] The polytetrafluoroethylene preferably has a core-shell structure.

[0018] The polytetrafluoroethylene preferably has an average primary particle size of 500 nm or less.

[0019] The polytetrafluoroethylene preferably has a primary particle aspect ratio of 1.45 or less. [Effects of the Invention]

[0020] According to the present disclosure, it is possible to produce polytetrafluoroethylene by polymerization using a hydrocarbon-based surfactant, and further to provide a production method that can produce polytetrafluoroethylene having a small average primary particle size despite the polymerization using a hydrocarbon-based surfactant. DETAILED DESCRIPTION OF THE INVENTION

[0021] In this specification, unless otherwise specified, the term "organic group" means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. Examples of the "organic group" are: an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents; cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, and RaOSO2- (In these formulas, Ra independently represents: an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents Includes. The organic group is preferably an alkyl group which may have one or more substituents. In this specification, unless otherwise specified, the term "substituent" refers to a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an and hydroxy groups, cyano groups, sulfo groups, carboxy groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, and diaromatic oxyphosphinyl groups.

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

[0023] The aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

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

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

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

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

[0028] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, and an N-phenylcarbamoyl group.

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

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

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

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

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

[0034] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 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, and a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total, 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, and 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, and a 4-pyridine sulfamoyl group.

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

[0036] The aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused with the aryl group, an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

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

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

[0039] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0040] The method for producing polytetrafluoroethylene [PTFE] of the present disclosure includes a polymerization step of obtaining PTFE by polymerizing tetrafluoroethylene [TFE] and a modifying monomer in an aqueous medium in the presence of a hydrocarbon surfactant. Therefore, according to the production method of the present disclosure, polytetrafluoroethylene can be produced by polymerization using a hydrocarbon surfactant. Furthermore, in the production method of the present disclosure, at the start of polymerization, more than 50 ppm of hydrocarbon surfactant is present in the aqueous medium. This allows the production of polytetrafluoroethylene with a small average primary particle size and a small aspect ratio. That is, polymerization of TFE and a modified monomer in an aqueous medium usually produces an aqueous dispersion containing polytetrafluoroethylene particles. However, according to the production method of the present disclosure, even though TFE and a modified monomer are polymerized using a hydrocarbon surfactant, particles with a small average primary particle size and a small aspect ratio are obtained, and an aqueous dispersion with excellent dispersion stability can be obtained. Furthermore, by coagulating the aqueous dispersion, polytetrafluoroethylene powder can be recovered, and polytetrafluoroethylene (uncoagulated polymer) is unlikely to remain in the wastewater remaining after the powder is recovered.

[0041] The PTFE contains 99.0% by mass or more of polymerized units based on TFE and 1.0% by mass or less of polymerized units based on a modifying monomer, and is also called modified PTFE.

[0042] The PTFE preferably contains polymerized units based on a modified monomer (hereinafter also referred to as "modified monomer units") in a range of 0.00001 to 1.0% by mass relative to the total polymerized units of the PTFE. The lower limit of the modified monomer unit content is preferably 0.0001% by mass, more preferably 0.0005% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit of the modified monomer unit content is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, especially preferably 0.10% by mass, particularly preferably 0.08% by mass, especially preferably 0.05% by mass, and more preferably 0.01% by mass. In this specification, the modified monomer unit means a part of the molecular structure of PTFE that is derived from the modified monomer.

[0043] In this specification, the content of each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0044] The modifying monomer is not particularly limited as long as it is copolymerizable with TFE, and examples thereof include fluoromonomers and non-fluoromonomers. The modifying monomer used may be one type or multiple types.

[0045] The non-fluoromonomer is not particularly limited and may be selected from the group consisting of monomers having the general formula: CH2=CR Q1 -LR Q2 (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 R Q2 R represents the bond position with Q2 represents a hydrogen atom, an alkyl group or a nitrile group.

[0046] Examples of non-fluoromonomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, vinyl methacrylate, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, ethyl vinyl ether, cyclohexyl vinyl ether, etc. Of these, butyl methacrylate, vinyl acetate, and acrylic acid are preferred as non-fluoromonomers.

[0047] Examples of fluoromonomers include perfluoroolefins such as hexafluoropropylene (HFP); hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF); perhaloolefins such as chlorotrifluoroethylene; perfluorovinyl ethers; and (perfluoroalkyl)ethylenes.

[0048] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (A): CF2=CF-ORf (A) (wherein Rf represents a perfluoroorganic group). In this specification, the "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0049] An example of the perfluorovinyl ether is perfluoro(alkyl vinyl ether) [PAVE], where Rf in the general formula (A) is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0050] Examples of the perfluoroalkyl group in the PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0051] The perfluorovinyl ether further includes those in which Rf in the general formula (A) is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and those in which Rf ...

[0052] [ka]

[0053] (wherein m represents 0 or an integer of 1 to 4), and Rf is a group represented by the following formula:

[0054] [ka]

[0055] (wherein n represents an integer of 1 to 4).

[0056] Examples of hydrogen-containing fluoroolefins include CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E-isomer), and CHF=CHCF3 (Z-isomer).

[0057] The (perfluoroalkyl)ethylene (PFAE) is not particularly limited, and examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.

[0058] A preferred example of the modifying monomer is the modifying monomer (3) having a monomer reactivity ratio of 0.1 to 8. The presence of the modifying monomer (3) makes it possible to obtain PTFE particles having a small particle size and an aqueous dispersion with high dispersion stability.

[0059] Here, the monomer reactivity ratio in copolymerization with TFE is the value obtained by dividing the rate constant when the propagating radical reacts with TFE when the propagating radical is less than a repeating unit based on TFE by the rate constant when the propagating radical reacts with the modified monomer. The lower this value, the higher the reactivity of the modified monomer with TFE. The monomer reactivity ratio can be calculated by copolymerizing TFE and the modified monomer, determining the composition in the resulting polymer immediately after the start of copolymerization, and using the Feynman-Ross equation.

[0060] The copolymerization was carried out in a 6.0 L stainless steel autoclave using 3600 g of deionized, degassed water, 1000 ppm ammonium perfluorooctanoate relative to the water, and 100 g of paraffin wax 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 were added to the reactor, respectively, and 0.072 g of ammonium persulfate (20 ppm relative to the water) was added. TFE was continuously fed to maintain the polymerization pressure at 0.78 MPa. When the TFE charge reached 1000 g, stirring was stopped and the reactor was depressurized until atmospheric pressure was reached. After cooling, the paraffin wax was separated to obtain an aqueous dispersion containing the resulting polymer. The aqueous dispersion was stirred to coagulate the resulting polymer, which was then dried at 150°C. The composition of the resulting polymer is calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0061] The modified monomer (3) having a monomer reactivity ratio of 0.1 to 8 is preferably at least one selected from the group consisting of modified monomers represented by formulas (3a) to (3d). CH2=CH-Rf 1 (3a) (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms. CF2=CF-O-Rf 2 (3b) (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 2 carbon atoms. CF2=CF-O-(CF2) n CF=CF2(3c) (wherein n is 1 or 2).

[0062] [ka] (In the formula, X 3 and X 4 is F, Cl or a methoxy group, and Y is of formula Y1 or Y2.

[0063] [ka] (In formula Y2, Z and Z′ are F or a fluorinated alkyl group having 1 to 3 carbon atoms.)

[0064] The content of the modifying monomer (3) units is preferably in the range of 0.00001 to 1.0% by mass relative to the total polymerized units of PTFE. The lower limit is more preferably 0.0001% by mass, more preferably 0.0005% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, especially preferably 0.10% by mass, particularly preferably 0.08% by mass, especially preferably 0.05% by mass, and more preferably 0.01% by mass.

[0065] As the above-mentioned modified monomer, since it can obtain an aqueous dispersion of modified polytetrafluoroethylene particles with a small average primary particle size, a small aspect ratio of primary particles, and excellent stability, it is preferable to select at least one from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, ethylene, and modified monomers having a functional group capable of reacting by radical polymerization and a hydrophilic group.By using the above-mentioned modified monomer, it is possible to obtain an aqueous dispersion of PTFE with a smaller average primary particle size, a small aspect ratio of primary particles, and excellent dispersion stability.In addition, it is possible to obtain an aqueous dispersion with less uncoagulated polymer.

[0066] From the viewpoint of reactivity with TFE, the modifying monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene. More preferably, it contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), (perfluorobutyl)ethylene, (perfluorohexyl)ethylene, and (perfluorooctyl)ethylene. The total amount of the hexafluoropropylene units, perfluoro(alkyl vinyl ether) units, and (perfluoroalkyl)ethylene units is preferably in the range of 0.00001 to 1% by mass relative to the total polymerized units of PTFE. The lower limit of the total amount is more preferably 0.0001% by mass, more preferably 0.0005% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, especially preferably 0.10% by mass, particularly preferably 0.08% by mass, especially preferably 0.05% by mass, and more preferably 0.01% by mass.

[0067] The above-mentioned modified monomer preferably includes a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group (hereinafter referred to as "modified monomer (A)").

[0068] The presence of the above-mentioned modifying monomer (A) can produce PTFE particles with a small primary particle size, and can produce an aqueous dispersion with high dispersion stability. In addition, the amount of uncoagulated polymer can be reduced. Furthermore, the aspect ratio of the primary particles can be reduced.

[0069] The amount of the modified monomer (A) used is preferably more than the amount corresponding to 0.1 ppm of the aqueous medium, more preferably more than 0.5 ppm, even more preferably more than 1.0 ppm, even more preferably 5 ppm or more, and particularly preferably 10 ppm or more. If the amount of the modified monomer (A) used is too small, the average primary particle size of the obtained PTFE may not be reduced. The amount of the modified monomer (A) used may be within the above range, but the upper limit can be, for example, 5000 ppm. In the above production method, the modified monomer (A) may be added to the system during the reaction to improve the stability of the aqueous dispersion during or after the reaction.

[0070] The above-mentioned modified monomer (A) is highly water-soluble, so even if unreacted modified monomer (A) remains in the aqueous dispersion, it can be easily removed in the concentration step or the coagulation and washing step.

[0071] The above-mentioned modifying monomer (A) is incorporated into the produced polymer during the polymerization process, but since the concentration of the modifying monomer (A) itself in the polymerization system is low and the amount incorporated into the polymer is small, there are no problems such as a decrease in the heat resistance of PTFE or coloration after baking.

[0072] Examples of the hydrophilic group in the modified monomer (A) include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (in each formula, M represents H, a metal atom, or NR 7y 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7y are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. ) are examples of the hydrophilic group. Of these, -SO3M or -COOM is preferred. R 7y The organic group in R is preferably an alkyl group. 7y As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the formula: The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (Group 1) or an alkaline earth metal (Group 2), with Na, K, or Li being preferred.

[0073] Examples of the "functional group capable of reacting by radical polymerization" in the modifying monomer (A) include groups having an ethylenically unsaturated bond, such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond is a group represented by the following formula: CX e X g =CX f R- (In the formula, X e , X f and X g are each independently F, Cl, H, CF3, CF2H, CFH2, or CH3; and R is a linking group. The linking group for R can be represented by the formula: a Preferred linking groups include -CH=CH2 and -CF=CH 2、 -CH=CF 2、 Examples include groups having an unsaturated bond such as -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CH=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, and -O-CF2-CF=CF2.

[0074] The modified monomer (A) has a functional group capable of reacting by radical polymerization, and therefore, when used in the polymerization, it is presumed that it reacts with the fluorine-containing monomer at the initial stage of the polymerization reaction, and forms highly stable particles having hydrophilic groups derived from the modified monomer (A). Therefore, it is considered that the number of particles increases when polymerization is carried out in the presence of the modified monomer (A).

[0075] The polymerization may be carried out in the presence of one type of the modifying monomer (A), or in the presence of two or more types thereof.

[0076] In the above polymerization, a compound having an unsaturated bond can be used as the modifying monomer (A).

[0077] The modifying monomer (A) is represented by the general formula (4): CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (4) (In the formula, X i , X j and X k are each independently F, Cl, H, or CF; Y 3 is a hydrophilic group; R a is a linking group; Z 1 and Z 2 are each independently H, F or CF3, and k is 0 or 1). Examples of the hydrophilic group include -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, and -COOM (in each formula, M represents H, a metal atom, or NR 7y 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7y are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. ) are examples of the hydrophilic group. Of these, -SO3M or -COOM is preferred. R 7y The organic group in R is preferably an alkyl group. 7y As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the following formula: Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K or Li being preferred. By using the modifying monomer (A), an aqueous dispersion having a smaller average primary particle size and better stability can be obtained, and the aspect ratio of the primary particles can also be made smaller.

[0078] Above R a is a linking group. In this specification, the term "linking group" refers to a divalent linking group. The linking group may be a single bond and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. There is no upper limit, but it may be, for example, 100 or less, or 50 or less. The linking group may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and may optionally contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may optionally contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate. The linking group may not contain carbon atoms but may be a catenary heteroatom such as oxygen, sulfur, or nitrogen.

[0079] Above R a is preferably a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group. R a When R is a divalent organic group, the hydrogen atom bonded to the carbon atom may be replaced with a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. a may be either linear or branched, and may be either cyclic or acyclic. a may contain functional groups (e.g., esters, ethers, ketones, amines, halides, etc.). R a may also be a non-fluorinated divalent organic group, or a partially fluorinated or perfluorinated divalent organic group. R aExamples of the hydrocarbon group include a hydrocarbon group in which no fluorine atoms are bonded to a carbon atom, a hydrocarbon group in which some of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms, a hydrocarbon group in which all of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms, -(C=O)-, -(C=O)-O-, or a hydrocarbon group containing -(C=O)-, which may contain an oxygen atom, a double bond, or a functional group.

[0080] R a is preferably —(C═O)—, —(C═O)—O—, or a hydrocarbon group having 1 to 100 carbon atoms which may contain an ether bond and may contain a carbonyl group, and in the hydrocarbon group, some or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine. R a Preferably, -(CH2) a -, -(CF2) a -, -O-(CF2) a -, -(CF2) a -O-(CF2) b -, -O(CF2) a -O-(CF2) b -, -(CF2) a -[O-(CF2) b ] c -, -O(CF2) a -[O-(CF2) b ] c -, -[(CF2) a -O] b -[(CF2) c -O] d -, -O[(CF2) a -O] b -[(CF2) c -O] d -, -O-[CF2CF(CF3)O] a -(CF2) b -, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2) a -, -(C=O)-(CF2) a -, -(C=O)-O-(CH2) a -, -(C=O)-O-(CF2) a-, -(C=O)-[(CH2) a -O] b -, -(C=O)-[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -, -(C=O)-O[(CF2) a -O] b -, -(C=O)-O[(CH2) a -O] b -(CH2) c -, -(C=O)-O[(CF2) a -O] b -(CF2) c -, -(C=O)-(CH2) a -O-(CH2) b -, -(C=O)-(CF2) a -O-(CF2) b -, -(C=O)-O-(CH2) a -O-(CH2) b -, -(C=O)-O-(CF2) a -O-(CF2) b At least one selected from -, -(C=O)-O-C6H4-, and combinations thereof. In the formula, a, b, c, and d are independently at least 1. a, b, c, and d may independently be 2 or more, 3 or more, 4 or more, 10 or more, or 20 or more. The upper limit of a, b, c, and d is, for example, 100.

[0081] R aSpecific examples suitable as -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3) CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CH2-, -(C=O)-, -(C=O)-O-, -(C=O)- (CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -, -(C=O)-[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CF2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-(CH2)2-O-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-, -(C=O)-O-C6H4-, etc. a Specifically, -CF2-O-, -CF2-O-CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2 -O-CF(CF3)CF2-O-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-O-(CH2)-, -(C=O)-O[(CH2)2-O] n -, -(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-(CH2)2-O-(CH2)-, or -(C=O)-O-C6H4- is preferred. In the above formula, n is an integer of 1 to 10.

[0082] -R in the above general formula (4) a -(CZ 1 Z 2) k -としては、-CF2-O-CF2-、-CF2-O-CF(CF3)-、-CF2-OC(CF3)2-、-CF2-O-CF2-CF2-、-CF2-O-CF2-CF(CF3)-、-CF2-O-CF2-C(CF3)2-、-CF2-O-CF2CF2-CF2-、-CF2-O-CF2CF2-CF (CF3)-、-CF2-O-CF2CF2-C(CF3)2-、-CF2-O-CF(CF3)-CF2-、-CF2-O-CF(CF3)-CF(CF 3)-、-CF2-O-CF(CF3)-C(CF3)2-、-CF2-O-CF(CF3)-CF2-、-CF2-O-CF(CF3)-CF(CF3) -、-CF2-O-CF(CF3)-C(CF3)2-、-CF2-O-CF(CF3)CF2-CF2-、-CF2-O-CF(CF3)CF2-CF( CF3)-、-CF2-O-CF(CF3)CF2-C(CF3)2-、-CF2-O-CF(CF3)CF2-O-CF2-、-CF2-O-CF(CF 3)CF2-O-CF(CF3)-、-CF2-O-CF(CF3)CF2-OC(CF3)2-、-(C=O)-、-(C=O)-O-、-(C=O)- (CH2)-、-(C=O)-(CF2)-、-(C=O)-O-(CH2)-、-(C=O)-O-(CF2)-、-(C=O)-[(CH2)2-O] n -(CH2)-、-(C=O)-[(CF2)2-O] n -(CF2)-、-(C=O)-[(CH2)2-O] n -(CH2)-(CH2)-、-(C=O)-[(CF2)2-O] n -(CF2)-(CF2)-、-(C=O)-O[(CH2)2-O] n -(CF2)-、-(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-、-(C=O)-O[(CF2)2-O] n -(CF2)-、-(C=O)-O[(CF2)2-O] n-(CF2)-(CF2)-, -(C=O)-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-(CH2)-, -(C=O )-O-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, -(C=O)-O-(CF2)2-O-(CF2)-C(CF3)2-, or -(C=O)-O-C6H4- C(CF3)2- is preferred, -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(C F3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -(C=O)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CH2)-(CH2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, or -(C=O)-O-C6H4-C(CF3)2- is more preferred. In the above formula, n is an integer of 1 to 10.

[0083] Specific examples of the compound represented by general formula (4) include: [ka] (In the formula, X j and Y 3 is the same as above. n is an integer of 1 to 10.

[0084] R a The following general formula (r1): -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g - (r1) (In the formula, X 6are each independently H, F, or CF3, e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1), and a divalent group represented by the following general formula (r2): -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g - (r2) (In the formula, X 7 are each independently H, F or CF3, e is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1. Divalent groups represented by the following formula are also preferred.

[0085] -R in the above general formula (4) a -(CZ 1 Z 2 ) k - can also be represented by the following formula (t1): -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 - (t1) (In the formula, X 6 are each independently H, F, or CF3, e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, and Z 1 and Z 2 are each independently F or CF3), and in formula (t1), Z 1 and Z 2 More preferably, one is F and the other is CF3. In addition, in the above general formula (4), -R a -(CZ 1 Z 2 ) k - is the following formula (t2): -(C=O) h -(O) i-CF2-O-(CX 7 2) e -(O) g -CZ 1 Z 2 - (t2) (In the formula, X 7 are each independently H, F, or CF3, e is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, and Z 1 and Z 2 are each independently H, F or CF3), and in formula (t2), Z 1 and Z 2 More preferably, one is F and the other is CF3.

[0086] The compound represented by the general formula (4) is a hydrophilic group (Y 3 ), it is also preferable that the compound has a C—F bond and does not have a C—H bond. i , X j , and X k All of the are F and R a is preferably a perfluoroalkylene group having one or more carbon atoms, and the perfluoroalkylene group may be either linear or branched, may be cyclic or acyclic, and may contain at least one catenary heteroatom. The number of carbon atoms in the perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0087] The compound represented by the general formula (4) may be partially fluorinated. That is, the compound represented by the general formula (4) may have a hydrophilic group (Y 3 ), it is also preferred that the alkyl group has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0088] The compound represented by general formula (4) is also preferably a compound represented by the following formula (4a). CF2=CF-O-Rf 0 -Y 3 (4a) (In the formula, Y3 is a hydrophilic group, and Rf 0 is a perfluorinated divalent linking group which may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and which optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0089] The compound represented by general formula (4) is also preferably a compound represented by the following formula (4b). CH2=CH-O-Rf 0 -Y 3 (4b) (In the formula, Y 3 is a hydrophilic group, and Rf 0 is a perfluorinated divalent linking group defined by formula (4a).

[0090] In general formula (4), Y 3 One of the preferred embodiments is -OSO3M. 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(OCF2CF2SON(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SON(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), and the like. In the above formulas, M is the same as above.

[0091] In general formula (4), Y 3 Another preferred form is -SO3M. 3is -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 above.

[0092] In general formula (4), Y 3 -COOM is also a preferred form. 3 is -COOM, the compounds represented by general formula (4) 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 is greater than 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(OCF2 CF(CF3)OCF2CF2SO2NR'CH2COOM), CH2=CH(CF2CF2SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR'CH2COOM), CH2=CH((CF2)4SO2NR'CH2COOM), CH2=CH(CF2CF2SO2NR'CH2COOM), CH2=CH((CF2)4SO2NR'CH2COOM), etc. In the above formula, R' represents H or C 1-4 is an alkyl group, and M is the same as above.

[0093] In general formula (4), Y 3 In another preferred embodiment, Y is -OPO3M. 3 is -OPO3M, examples of the compound represented by general formula (4) 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)CH2CH2 OP(O)(OM)), CF=CF(OCFCFCFCFSON(CH)CHCHOP(O)(OM)), CH=CH(CFCFCHOP(O)(OM)), CH=CH((CF)CHOP(O)(OM)), CH=CH(CFCFCHOP(O)(OM)), CH=CH((CF)CHOP(O)(OM)). In the above formula, M is the same as above.

[0094] In general formula (4), Y 3 In another preferred embodiment, Y is -PO3M. 3 is -PO3M, examples of the compound represented by general formula (4) 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), and the like, where M is the same as above.

[0095] The compound represented by the above general formula (4) includes compounds represented by the following general formula (5): CX2=CY(-CZ2-O-Rf-Y 3 ) (5) (In the formula, X's may be the same or different and each represent -H or -F; Y's may be -H, -F, an alkyl group or a fluorine-containing alkyl group; and Z's may be the same or different and each represent -H, -F, an alkyl group or a fluorine-containing alkyl group. Rf's may be a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. Y 3 is the same as above, a monomer represented by the following general formula (6): CX2=CY(-O-Rf-Y 3 ) (6) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; and Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. Y 3 is the same as above.) and a monomer represented by the following general formula (7): CX2=CY(-Rf-Y 3 ) (7) (In the formula, X may be the same or different and is -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; and Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. Y 3 is the same as above. Preferably, the monomer is at least one selected from the group consisting of: The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0096] In the above general formula (5), X is -H or -F. Both Xs may be -F, or at least one X may be -H. For example, one X may be -F and the other may be -H, or both Xs may be -H.

[0097] In the above general formula (5), Y is —H, —F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms. The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have a carbon number of at least 1. The fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms. The above Y is preferably -H, -F or -CF3, and more preferably -F.

[0098] In the above general formula (5), Z may be the same or different and is —H, —F, an alkyl group or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms. The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have a carbon number of at least 1. The fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms. The above Z is preferably -H, -F or -CF3, and more preferably -F.

[0099] In the general formula (5), it is preferable that at least one of X, Y, and Z contains a fluorine atom. For example, X may be —H, and Y and Z may be —F.

[0100] In the general formula (5), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. Also, it is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0101] The carbon number of the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The carbon number of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less. Examples of the fluorine-containing alkylene group having an ether bond include a group represented by the following formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is also preferably a divalent group represented by the formula: H, F, or CF3; p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5). Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)- (wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0102] In the above general formula (5), Y 3 is -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7y 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7y are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. R 7y The organic group in is preferably an alkyl group. R 7y As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the formula: The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li. The above M is —H, a metal atom, or —NR 7y 4 is preferred, and -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7y 4 is more preferred, -H, -Na, -K, -Li or -NH4 is even more preferred, -Na, -K or -NH4 is even more preferred, -Na or -NH4 is especially preferred, and -NH4 is most preferred. Above Y 3 As the alkyl group, -COOM or -SO3M is preferred, and -COOM is more preferred.

[0103] The monomer represented by the general formula (5) is preferably a monomer (5a) represented by the following general formula (5a). CH2=CF(-CF2-O-Rf-Y 3 ) (5a) (Wherein Rf and Y 3 is the same as above.)

[0104] Specific examples of the monomer represented by the general formula (5a) include those represented by the following formula:

[0105] [ka]

[0106] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is H, F, or CF3; p1+q1+r1 are integers between 0 and 10; s1 is 0 or 1; t1 is an integer between 0 and 5; Y 3 is the same as above, except for Z 3 and Z 4 are both H, then p1+q1+r1+s1 is not 0). More specifically,

[0107] [ka]

[0108] Among them,

[0109] [ka]

[0110] It is preferable that:

[0111] The monomer represented by the general formula (5a) includes, for example, Y 3 is preferably -COOM, and particularly preferably at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is as defined above), and more preferably CH2=CFCF2OCF(CF3)COOM.

[0112] The monomer represented by the general formula (5) is preferably a monomer (5b) represented by the following general formula (5b). CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y3 (5b) (In the formula, each 2 are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, and Y 3 is the same as the definition above.)

[0113] In the formula (5b), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, from the viewpoint of the stability of the resulting aqueous dispersion. 3 -COOM is advantageous in that it provides moderate water solubility and stability of aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0114] Examples of the perfluorovinyl alkyl compound represented by the above formula (5b) include CH2=CFCF2OCF(CF3)COOM 1 , CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM 1 (In the formula, M 1 is the same as the definition above.

[0115] Further, examples of the monomer represented by the general formula (5) include a monomer represented by the following general formula (5c).

[0116] CF2=CFCF2-O-Rf-Y 3 (5c) (Wherein Rf and Y 3 is the same as above)

[0117] More specifically, [ka] etc.

[0118] In the above general formula (6), X is -H or -F. Both Xs may be -F, or at least one X may be -H. For example, one X may be -F and the other may be -H, or both Xs may be -H.

[0119] In the above general formula (6), Y is —H, —F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have a carbon number of at least 1. The alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms. The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have a carbon number of at least 1. The fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms. The above Y is preferably -H, -F or -CF3, and more preferably -F.

[0120] In the general formula (6), it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be —H, and Y and Z may be —F.

[0121] In the general formula (6), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. The number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Examples of the fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, and -CF(CF3)CH2-. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0122] The monomer represented by the general formula (6) is preferably at least one selected from the group consisting of monomers represented by the following general formulae (6a), (6b), (6c), (6d) and (6e): CF2=CF-O-(CF2) n1 -Y 3 (6a) (wherein n1 represents an integer of 1 to 10, and Y 3 -SO3M 1 or -COOM 1 represents M 1 is H, metal atom, NR 7y 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7y represents H or an organic group. CF2=CF-O-(CF2C(CF3)F) n2 -Y 3 (6b) (wherein n2 represents an integer of 1 to 5, and Y 3 is the same as the definition above.) CF2=CF-O-(CFX 1 ) n3 -Y 3 (6c) (In the formula, X 1 represents F or CF3, n3 represents an integer of 1 to 10, and Y 3 is the same as the definition above.) CF2=CF-O-(CF2CFX 1 O) n4 -CF2CF2-Y 3 (6d) (wherein n4 represents an integer of 1 to 10, and Y 3 and X 1 is the same as the definition above.) CF2=CF-O-(CF2CF2CFX 1 O) n5 -CF2CF2CF2-Y 3 (6e) (wherein n5 represents an integer of 0 to 10, and Y 3 and X 1 is the same as the definition above.)

[0123] In the formula (6a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. 3 -COOM is advantageous in that it can provide adequate water solubility and stability of the aqueous dispersion. 1 Preferably, M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0124] The monomer represented by the above formula (6a) is, for example, CF2=CF-O-CF2COOM 1 (In the formula, M 1 is the same as the definition above.

[0125] In the formula (6b), n2 is preferably an integer of 3 or less in terms of the stability of the resulting aqueous dispersion, and Y 3 -COOM is advantageous in that it provides adequate water solubility and stability of the aqueous dispersion. 1 Preferably, M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0126] In the formula (6c), n3 is preferably an integer of 5 or less in terms of water solubility, and Y 3 -COOM is advantageous in that it provides adequate water solubility and stability of the aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4 in terms of improving dispersion stability.

[0127] In the above formula (6d), the above X 1 is preferably -CF3 from the viewpoint of stability of the aqueous dispersion, n4 is preferably an integer of 5 or less from the viewpoint of water solubility, and Y 3 -COOM is advantageous in that it provides moderate water solubility and stability of aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4.

[0128] Examples of the monomer represented by the above formula (6d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM 1 (In the formula, M 1 represents H, NH4 or an alkali metal.

[0129] In the general formula (6e), n5 is preferably an integer of 5 or less in terms of water solubility, and Y 3 -COOM is advantageous in that it provides moderate water solubility and stability of aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4.

[0130] Examples of the monomer represented by general formula (6e) include CF2=CFOCF2CF2CF2COOM 1 (In the formula, M 1 represents H, NH4 or an alkali metal.

[0131] In the above general formula (7), Rf is preferably a fluorine-containing alkylene group having a carbon number of 1 to 40. In general formula (7), at least one of X and Y preferably contains a fluorine atom.

[0132] The monomer represented by the above general formula (7) is represented by the following general formula (7a): CF2=CF-(CF2) n1 -Y 3 (7a) (wherein n1 represents an integer of 1 to 10, and Y 3 is as defined above.) and a monomer represented by the following general formula (7b): CF2=CF-(CF2C(CF3)F) n2 -Y 3 (7b) (wherein n2 represents an integer of 1 to 5, and Y 3 is as defined above. At least one selected from the group consisting of monomers represented by Above Y 3 -SO3M 1 or -COOM 1is preferred, and M 1 is H, metal atom, NR 7y 4. It is preferably an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 7y represents H or an organic group.

[0133] In the formula (7a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. 3 -COOM is advantageous in that it can provide adequate water solubility and stability of the aqueous dispersion. 1 Preferably, M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved. The perfluorovinyl alkyl compound represented by the above formula (7a) is, for example, CF2=CFCF2COOM 1 (In the formula, M 1 is the same as the definition above.

[0134] In the formula (7b), n2 is preferably an integer of 3 or less in terms of the stability of the resulting aqueous dispersion, and Y 3 -COOM is advantageous in that it provides adequate water solubility and stability of the aqueous dispersion. 1 Preferably, M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0135] The above-mentioned modified monomer preferably contains modified monomer (A), and preferably contains at least one selected from the group consisting of compounds represented by general formula (5c), general formula (6a), general formula (6b), general formula (6c), and general formula (6d), and more preferably contains a compound represented by general formula (5c).

[0136] When the modifying monomer includes the modifying monomer (A), the content of polymerized units based on the modifying monomer (A) is preferably in the range of 0.00001 to 1.0% by mass relative to the total polymerized units of PTFE. The lower limit is preferably 0.0001% by mass, more preferably 0.0005% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, especially preferably 0.10% by mass, particularly preferably 0.08% by mass, especially preferably 0.05% by mass, and more preferably 0.01% by mass.

[0137] The PTFE may have a core-shell structure, which is a conventionally known structure and is the structure of primary particles in an aqueous dispersion that can be produced by the method described in U.S. Pat. No. 6,841,594 or the like. Examples of polytetrafluoroethylene having a core-shell structure include a core-shell structure comprising a core portion of a TFE homopolymer and a shell portion of a modified PTFE, a core-shell structure comprising a core portion of a modified PTFE and a shell portion of a TFE homopolymer, and a core-shell structure comprising a core portion of a modified PTFE and a shell portion of a modified PTFE having a different monomer composition from the modified PTFE that constitutes the core portion. The PTFE having the core-shell structure can be obtained, for example, by first polymerizing TFE and, if necessary, a modified monomer to produce a core portion (TFE homopolymer or modified PTFE), and then polymerizing TFE and, if necessary, a modified monomer to produce a shell portion (TFE homopolymer or modified PTFE). The shell portion means a portion that constitutes a predetermined thickness from the surface of the PTFE primary particle to the interior of the particle, and the core portion means a portion that constitutes the interior of the shell portion.

[0138] In this specification, the core-shell structure includes all of the following: (1) a structure in which the core and shell portions have different monomer compositions; (2) a structure in which the core and shell portions have the same monomer composition but different number-average molecular weights; and (3) a structure in which the core and shell portions have different monomer compositions but different number-average molecular weights.

[0139] When the shell portion is modified PTFE, the content of the modifying monomer in the shell portion is preferably 0.00001 to 1.0% by mass, more preferably 0.0001% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more. Also, it is more preferably 0.50% by mass or less, and even more preferably 0.30% by mass or less.

[0140] When the core part is modified PTFE, the content of the modifying monomer in the core part is preferably 0.00001 to 1.0% by mass, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more, and more preferably 0.50% by mass or less, and even more preferably 0.30% by mass or less.

[0141] The PTFE preferably has an average primary particle diameter of 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less. PTFE with a small average primary particle diameter can be obtained by the manufacturing method of the present disclosure. The lower limit of the average primary particle diameter is not particularly limited, but may be, for example, 50 nm or 100 nm. From the viewpoint 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. The average primary particle size can be measured by dynamic light scattering. A PTFE aqueous dispersion adjusted to a solids concentration of approximately 1.0% by mass is prepared, and the average primary particle size is measured by dynamic light scattering at 25°C, with a solvent (water) refractive index of 1.3328 and a solvent (water) viscosity of 0.8878 mPa·s, and 70 cumulative measurements. For example, an ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) can be used for the dynamic light scattering method.

[0142] The PTFE preferably has a primary particle aspect ratio of 1.45 or less, more preferably 1.40 or less, even more preferably 1.35 or less, even more preferably 1.30 or less, especially preferably 1.25 or less, particularly preferably 1.20 or less, and especially especially preferably 1.15 or less. When measuring in an aqueous dispersion, the aspect ratio is determined by observing an aqueous PTFE dispersion diluted to a solids concentration of approximately 1% by mass with a scanning electron microscope (SEM), processing images of at least 400 randomly selected particles, and averaging the ratio of their major axis to their minor axis. When measuring in powder, the aspect ratio can be obtained by irradiating PTFE powder with an electron beam, adding it to an aqueous fluorosurfactant solution, and redispersing it with ultrasound to obtain an aqueous PTFE dispersion. The aspect ratio is then determined from this aqueous PTFE dispersion using the same method as for measuring the aqueous dispersion described above.

[0143] The standard specific gravity (SSG) of the PTFE is preferably 2.280 or less, more preferably 2.200 or less, even more preferably 2.190 or less, and even more preferably 2.180 or less. Preferably, it is 2.130 or more. The SSG is measured by the water displacement method according to ASTM D-792 using a sample molded according to ASTM D 4895-89.

[0144] The PTFE may have a thermal instability index (TII) of 20 or more. Such PTFE can be obtained by using a hydrocarbon surfactant. The TII is preferably 25 or more, more preferably 30 or more, and even more preferably 35 or more. It is particularly preferably 40 or more. The TII is measured in accordance with ASTM D 4895-89.

[0145] The PTFE may have a 0.1% mass loss temperature of 400°C or lower. Such PTFE can be obtained by using a hydrocarbon surfactant. The 0.1% mass loss temperature is a value measured by the following method. Approximately 10 mg of PTFE powder that had not been heated to temperatures above 300°C was precisely weighed, placed in a special aluminum pan, and measured using a TG / DTA (thermogravimetric differential thermal analyzer). The 0.1% mass loss temperature was determined as the temperature at which a 0.1 mass% weight loss occurred when the aluminum pan was heated in an air atmosphere from 25°C to 600°C at a rate of 10°C / min.

[0146] The PTFE may have a 1.0% mass loss temperature of 492°C or lower. Such PTFE can be obtained by using a hydrocarbon surfactant. The 1.0% mass loss temperature is a value measured by the following method. Approximately 10 mg of PTFE powder that had not been heated to temperatures above 300°C was precisely weighed, placed in a special aluminum pan, and measured using a TG / DTA (thermogravimetric differential thermal analyzer). The 1.0% mass loss temperature was determined as the temperature at which a 1.0 mass% weight loss occurred when the aluminum pan was heated in an air atmosphere from 25°C to 600°C at a rate of 10°C / min.

[0147] The PTFE preferably has a peak temperature of not more than 342° C., more preferably not more than 341° C., and even more preferably not more than 340° C. The peak temperature is a value measured by the following method. Approximately 10 mg of powder that has not been heated to temperatures above 300°C is precisely weighed, placed in a special aluminum pan, and measured using a TG / DTA (thermogravimetric differential thermal analyzer). The peak temperature is determined as the temperature corresponding to the maximum value of the differential thermal (DTA) curve when the aluminum pan is heated in an air atmosphere from 25°C to 600°C at a rate of 10°C / min.

[0148] The extrusion pressure of the PTFE is preferably 50.0 MPa or less, more preferably 40.0 MPa or less, and is preferably 5.0 MPa or more, more preferably 10.0 MPa or more, and even more preferably 15.0 MPa or more. The extrusion pressure is a value determined by the following method. 21.7 g of lubricant (trade name: Isopar H®, Exxon) was added to 100 g of PTFE powder and mixed for 3 minutes in a glass bottle at room temperature. The glass bottle was then left at room temperature (25°C) for at least 1 hour before extrusion to obtain a lubricated resin. The lubricated resin was paste-extruded through an orifice (diameter 2.5 mm, land length 11 mm, entrance angle 30°) at room temperature at a reduction ratio of 100:1 to obtain a uniform bead (extrusion molded product). The extrusion speed, i.e., ram speed, was 20 in / min (51 cm / min). The extrusion pressure was determined by measuring the load when the extrusion load reached equilibrium during paste extrusion and dividing it by the cross-sectional area of ​​the cylinder used for paste extrusion.

[0149] The PTFE generally has extensibility, fibrillation properties, and non-melt fabricability. The term "non-melt processable" means that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116, i.e., the polymer does not flow easily even in the melting temperature range.

[0150] The production method of the present disclosure includes a polymerization step of obtaining polytetrafluoroethylene by polymerizing tetrafluoroethylene and a modifying monomer in an aqueous medium in the presence of a hydrocarbon surfactant.

[0151] The polymerization temperature and polymerization pressure in the above polymerization step are appropriately determined depending on the type of monomer used, the desired molecular weight of PTFE, and the reaction rate. For example, the polymerization temperature is preferably 10 to 150° C. The polymerization temperature is more preferably 30° C. or higher, and even more preferably 50° C. or higher. The polymerization temperature is more preferably 120° C. or lower, and even more preferably 100° C. or lower. The polymerization pressure is preferably 0.05 to 10 MPa. The polymerization pressure is more preferably 0.3 MPa or higher, and even more preferably 0.5 MPa or higher. Also, it is more preferably 5.0 MPa or lower, and even more preferably 3.0 MPa or lower. In particular, from the viewpoint of improving the yield of PTFE, it is preferably 1.0 MPa or higher, more preferably 1.2 MPa or higher, even more preferably 1.5 MPa or higher, particularly preferably 1.8 MPa or higher, and particularly preferably 2.0 MPa or higher.

[0152] In the above polymerization step, the amount of hydrocarbon surfactant at the start of polymerization is more than 50 ppm relative to the aqueous medium. The amount of hydrocarbon surfactant at the start of polymerization is preferably 60 ppm or more, more preferably 70 ppm or more, even more preferably 80 ppm or more, even more preferably 100 ppm or more, particularly preferably 150 ppm or more, particularly preferably 200 ppm or more, and most preferably 300 ppm or more. The upper limit is not particularly limited, but for example, it is preferably 10,000 ppm, more preferably 5,000 ppm. By setting the amount of hydrocarbon surfactant at the start of polymerization within the above range, an aqueous dispersion with a smaller average primary particle size and better stability can be obtained. In addition, an aqueous dispersion with a smaller amount of uncoagulated polymer can be obtained. Furthermore, the aspect ratio of the primary particles can be made smaller.

[0153] Polymerization can be said to have begun when the gaseous fluoromonomer in the reactor becomes polytetrafluoroethylene and a pressure drop occurs in the reactor. U.S. Pat. No. 3,391,099 (Punderson) discloses dispersion polymerization of tetrafluoroethylene in an aqueous medium, which consists of two distinct stages in the polymerization process: first, the formation of polymer nuclei as nucleation sites, and then, the growth stage, which involves the polymerization of the established particles. Note that polymerization usually begins when both the monomer to be polymerized and the polymerization initiator are charged into the reactor. In this disclosure, the additive involved in the formation of nucleation sites is referred to as a nucleating agent.

[0154] The polymerization step is a step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a hydrocarbon surfactant, and it is also preferable that the step includes a step of continuously adding the hydrocarbon surfactant. Adding the hydrocarbon surfactant continuously means, for example, adding the hydrocarbon surfactant not all at once but over time, either continuously or in portions. In the step of continuously adding the hydrocarbon surfactant, it is preferable 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 hydrocarbon surfactant is more preferably started when the concentration is 0.50% by mass or less, even more preferably when it is 0.36% by mass or less, even more preferably when it is 0.30% by mass or less, even more preferably when it is 0.20% by mass or less, particularly preferably when it is 0.10% by mass or less, and most preferably when the polymerization starts. The above concentration is the concentration relative to the total of the aqueous medium and the PTFE. By including the above process, an aqueous dispersion having a smaller average primary particle size and excellent stability can be obtained. Also, an aqueous dispersion having a smaller amount of uncoagulated polymer can be obtained. Furthermore, the aspect ratio of the primary particles can be made smaller.

[0155] In the step of continuously adding the hydrocarbon surfactant, the amount of the hydrocarbon surfactant added is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium, more preferably 0.05% by mass at the lower limit, even more preferably 0.1% by mass at the lower limit, more preferably 5% by mass at the upper limit, and even more preferably 1% by mass at the upper limit.

[0156] In the step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of the hydrocarbon surfactant, the amount of the hydrocarbon surfactant is preferably large, and is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferred lower limit is 0.1% by mass, and a more preferred upper limit is 1% by mass.

[0157] The manufacturing method of the present disclosure preferably further includes a step of adding a modifying monomer to the aqueous medium before the start of polymerization or when the concentration of PTFE formed in the aqueous medium is 5.0% by mass or less. Adding the modifying monomer at the beginning of polymerization makes it possible to obtain an aqueous dispersion with a small average primary particle size, a small aspect ratio of the primary particles, and excellent stability. That is, the modifying monomer may be added before the start of polymerization, or may be added simultaneously with the start of polymerization. Alternatively, the modifying monomer may be added during the period in which PTFE particle nuclei are formed after the start of polymerization. For example, it is preferable to add the modifying monomer when the PTFE concentration is 5.0% by mass or less. The amount of the modifying 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 is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.003% by mass or more, based on the polytetrafluoroethylene obtained. The upper limit is not limited, but is, for example, 1.0% by mass.

[0158] In the above polymerization process, the number of PTFE particles was 6.0 × 10 12 By increasing the number of PTFE particles (nuclei) in the early stage of polymerization, an aqueous dispersion having a small average primary particle size, a small aspect ratio of the primary particles, and excellent stability can be obtained. The number of PTFE particles is preferably 7.0 × 10 12 More preferably, it is 8.0 × 10 12 More preferably, the number is 9.0 × 10 12More preferably, the number is 1.0 × 10 13 The upper limit is not particularly limited, but for example, 7.0 × 10 14 pieces / mL. In the polymerization process, 0.6 × 10 13 It is preferable to generate PTFE particles at a concentration of 0.7 × 10 or more per ml. 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. The number of PTFE particles to be generated is 0.7 × 10 13 More preferably, it is 0.8 × 10 13 More preferably, the number is 0.9 × 10 13 More preferably, the number is 1.0 × 10 13 The upper limit is not particularly limited, but for example, 7.0 × 10 14 pieces / mL. Since PTFE particles are generated intensively in the first half of the polymerization and are less likely to be generated in the second half of the polymerization, 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 PTFE aqueous dispersion.

[0159] As the hydrocarbon surfactant, for example, those described in JP-A Nos. 2013-542308, 2013-542309, and 2013-542310 can be used.

[0160] The hydrocarbon surfactants may be surfactants having a hydrophilic portion and a hydrophobic portion on the same molecule, and may be cationic, nonionic, or anionic.

[0161] Cationic hydrocarbon surfactants typically have a positively charged hydrophilic portion, such as an alkylated ammonium halide, such as an alkylated ammonium bromide, and a hydrophobic portion, such as a long-chain fatty acid.

[0162] Anionic hydrocarbon surfactants typically have a hydrophilic portion, such as a carboxylate, sulfonate, or sulfate, and a hydrophobic portion, which is a long chain hydrocarbon moiety, such as an alkyl.

[0163] Nonionic hydrocarbon surfactants typically contain no charged groups and have a hydrophobic portion that is a long hydrocarbon chain. The hydrophilic portion of the nonionic surfactant contains a water-soluble functional group, such as an ethylene ether chain derived from polymerization with ethylene oxide.

[0164] Examples of nonionic hydrocarbon surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

[0165] Specific examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene behenyl ether.

[0166] Specific examples of polyoxyethylene alkylphenyl ethers include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0167] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.

[0168] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0169] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0170] Specific examples of glycerol esters include glycerol monomyristate, glycerol monostearate, and glycerol monooleate.

[0171] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

[0172] The ethers and esters may have an HLB value of 10-18.

[0173] Examples of nonionic hydrocarbon surfactants include the Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), and Tergitol (registered trademark) L series, all manufactured by Dow Chemical Company; the Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m to 22, n to 23)) and the Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10), all manufactured by BASF.

[0174] Examples of anionic hydrocarbon surfactants include Versatic (registered trademark) 10 manufactured by Resolution Performance Products and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0175] The hydrocarbon surfactants include R Z -LM (where R Z is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may form a ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or NR 5Z 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 5Z is H or an organic group, -ArSO3 - is an aryl sulfonate. ) Specifically, CH3-(CH2) such as lauric acid n -LM (wherein n is an integer of 6 to 17, and L and M are the same as above). R Z A mixture in which is an alkyl group having 12 to 16 carbon atoms and LM is sulfate or sodium dodecyl sulfate (SDS) can also be used. Other surfactant compounds include R 6Z (-LM)2(wherein, R 6Z is a linear or branched alkylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms which may have a substituent, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or NR 5Z4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 5Z is H or an organic group, -ArSO3 - is an aryl sulfonate. ) The hydrocarbon surfactants include R 7Z (-LM)3(wherein, R 7Z is a linear or branched alkylidyne group having one or more carbon atoms which may have a substituent, or a cyclic alkylidyne group having three or more carbon atoms which may have a substituent, and when the number of carbon atoms is three or more, it may contain a monovalent or divalent heterocycle or may form a ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or NR 5Z 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 5Z is H or an organic group. -ArSO3 - is an aryl sulfonate. ) Above R 5z is preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and even more preferably H or an alkyl group having 1 to 4 carbon atoms. In this specification, unless otherwise specified, the term "substituent" refers to a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an and hydroxy groups, cyano groups, sulfo groups, carboxy groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, and diaromatic oxyphosphinyl groups.

[0176] The hydrocarbon surfactants also include siloxane hydrocarbon surfactants. Examples of siloxane hydrocarbon surfactants include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of siloxane hydrocarbon surfactants includes a distinct hydrophobic portion and a hydrophilic portion. The hydrophobic portion includes one or more dihydrocarbylsiloxane units, where the substituents on the silicone atom are completely hydrocarbons. These siloxane hydrocarbon surfactants can also be considered hydrocarbon surfactants in the sense that the carbon atoms of the hydrocarbyl groups, while potentially substituted by halogens such as fluorine, are fully substituted by hydrogen atoms, i.e., the monovalent substituents on the carbon atoms of the hydrocarbyl groups are hydrogen.

[0177] The hydrophilic portion of the siloxane hydrocarbon surfactant may comprise one or more polar moieties containing ionic groups such as sulfates, sulfonates, phosphonates, phosphate esters, carboxylates, carbonates, sulfosuccinates, taurates (as free acids, salts or esters), phosphine oxides, betaines, betaine copolyols, quaternary ammonium salts, etc. The ionic hydrophobic portion may also comprise ionically functionalized siloxane grafts. Examples of such siloxane hydrocarbon surfactants include polydimethylsiloxane-graft-(meth)acrylate salts, polydimethylsiloxane-graft-polyacrylate salts, and polydimethylsiloxane-grafted quaternary amines. The polar portion of the hydrophilic portion of the siloxane hydrocarbon surfactant may include nonionic groups formed by polyethers such as polyethylene oxide (PEO) and mixed polyethylene oxide / propylene oxide polyethers (PEO / PPO); monosaccharides and disaccharides; and water-soluble heterocycles such as pyrrolidinone. The ratio of ethylene oxide to propylene oxide (EO / PO) may be varied in mixed polyethylene oxide / propylene oxide polyethers.

[0178] The hydrophilic portion of the siloxane hydrocarbon surfactant may also contain a combination of ionic and nonionic moieties. Such moieties include, for example, ionically end-functionalized or randomly functionalized polyethers or polyols. Preferred for the practice of the present disclosure are siloxanes with nonionic moieties, i.e., nonionic siloxane surfactants.

[0179] The arrangement of hydrophobic and hydrophilic moieties in the structure of the siloxane hydrocarbon surfactant may take the form of a diblock polymer (AB), a triblock polymer (ABA) (where "B" represents the siloxane portion of the molecule), or a multiblock polymer. Alternatively, the siloxane surfactant may comprise a graft polymer.

[0180] Siloxane hydrocarbon surfactants are also disclosed in US Pat. No. 6,841,616.

[0181] Siloxane-based anionic hydrocarbon surfactants include SilSense, available from Noveon® Consumer Specialties of Lubrizol Advanced Materials, Inc. TM PE-100 Silicone, SilSense TM CA-1 silicone and the like.

[0182] Anionic hydrocarbon surfactants also include the sulfosuccinate surfactant Lankropol® K8300 from Akzo Nobel Surface Chemistry LLC. Sulfosuccinate surfactants include sodium diisodecyl sulfosuccinate (Emulsogen® SB10 from Clariant), sodium diisotridecyl sulfosuccinate (Polirol® TR / LNA from Cesapinia Chemicals), and the like.

[0183] The hydrocarbon surfactant may be PolyFox (registered trademark) surfactant from Omnova Solutions, Inc. TM PF-156A, PolyFox TM PF-136A, etc.)

[0184] The hydrocarbon surfactant is preferably an anionic hydrocarbon surfactant. The anionic hydrocarbon surfactants described above can be used, but for example, the following anionic hydrocarbon surfactants can be suitably used.

[0185] Examples of the anionic hydrocarbon surfactant include those represented by the following formula (α): R 100 -COOM (α) (In the formula, R 100is a monovalent organic group containing one or more carbon atoms. M is H, a metal atom, NR 101 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 101 R is H or an organic group, and may be the same or different. 101 The organic group in R is preferably an alkyl group. 101 is 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of surfactant activity, R 100 The number of carbon atoms in R is preferably 2 or more, and more preferably 3 or more. 100 The number of carbon atoms is preferably 29 or less, and more preferably 23 or less. The metal atom of M includes alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. M is H, a metal atom, or NR 101 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 101 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0186] The compound (α) includes R 102 -COOM(in the formula, R 102 is a linear or branched alkyl group, alkenyl group, alkylene group or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group, alkenyl group, alkylene group or alkenylene group having 3 or more carbon atoms which may have a substituent, and these may contain an ether bond. When the carbon number is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above. ) are also included. Specifically, CH3-(CH2) n-COOM (wherein n is an integer of 2 to 28, and M is the same as above).

[0187] From the viewpoint of emulsion stability, the compound (α) may not contain a carbonyl group (excluding a carbonyl group in a carboxyl group). Examples of the hydrocarbon-containing surfactant that does not contain a carbonyl group include surfactants represented by the following formula (A): R 103 -COO-M (A) (In the formula, R 103 is an alkyl group, an alkenyl group, an alkylene group, or an alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond; M is H, a metal atom, NR 101 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 101 are the same or different and are H or an organic group. In the above formula (A), R 103 is preferably an alkyl group or an alkenyl group (which may contain an ether group). 103 The alkyl group or alkenyl group in the above R may be linear or branched. 103 The number of carbon atoms is not limited, but is, for example, 2 to 29.

[0188] When the alkyl group is linear, R 103 The number of carbon atoms in R is preferably 3 to 29, and more preferably 5 to 23. When the alkyl group is branched, R 103 The number of carbon atoms is preferably 5 to 35, and more preferably 11 to 23. When the alkenyl group is linear, R 103 The number of carbon atoms in R is preferably 2 to 29, and more preferably 9 to 23. When the alkenyl group is branched, R 103 The number of carbon atoms is preferably 4 to 29, and more preferably 9 to 23.

[0189] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a t-butyl group, and a vinyl group.

[0190] Examples of the 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, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, mead acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, and croton Examples of suitable oleic acids include oleic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, osbondo acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, herring acid, and salts thereof. Particularly, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof is preferred. The salts include those in which the hydrogen of the carboxyl group is replaced by a metal atom of the formula M, NR 101 4. Examples include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. As the surfactant (α) (carboxylic acid type hydrocarbon surfactant), at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof is preferred, with lauric acid and salts thereof being more preferred, salts of lauric acid being particularly preferred, and sodium laurate and ammonium laurate being most preferred, because these surfactants can give particles with a small average primary particle size by polymerization and can generate a large number of particles during polymerization, thereby enabling efficient production of polytetrafluoroethylene.

[0191] The hydrocarbon surfactant may be a surfactant represented by the following general formula (1): [ka] (In the formula, R 1 ~R 5 represents H or a monovalent substituent, provided that R 1 and R 3 At least one of the groups has the general formula: -YR 6 a group represented by R 2 and R 5 At least one of the groups is a group represented by the general formula: -XA or a group represented by the general formula: -YR 6 represents a group represented by the formula: Furthermore, X, in each occurrence, is the same or different and represents a divalent linking group or a bond; A is the same or different in each occurrence and is -COOM, -SO3M, or -OSO3M (wherein M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group); Y may be the same or different in each occurrence and may be -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 a divalent linking group selected from the group consisting of CO—, or a bond, R 8 is H or an organic group; R 6are the same or different in each occurrence and each represents an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms; Represents. R 1 ~R 5 Any two of these may be bonded to each other to form a ring.) (hereinafter also referred to as surfactant (1)) is a preferred example.

[0192] The surfactant (1) will be explained.

[0193] In the formula, R 1 ~R 5 represents H or a monovalent substituent, provided that R 1 and R 3 At least one of the groups has the general formula: -YR 6 a group represented by R 2 and R 5 At least one of the groups is a group represented by the general formula: -XA or a group represented by the general formula: -YR 6 R represents a group represented by 1 ~R 5 Any two of these may be bonded to each other to form a ring.

[0194] R 1 The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0195] R 1 The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0196] R 1 As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0197] The monovalent substituent includes a group represented by the general formula: -YR 6 a group represented by the general formula: -XA; -H; optionally substituted C 1-20 Alkyl groups, -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.

[0198] R 9 As for C 1-10 or C 1-10 The alkylcarbonyl group of C is preferred. 1-4 or C 1-4 The alkylcarbonyl group of the formula is more preferred.

[0199] In the formula, X may be the same or different in each occurrence and represents a divalent linking group or bond. R 6When X does not contain 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 group selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0200] X may be -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, or -CONR 8 - and -NR 8 a divalent linking group containing at least one bond selected from the group consisting of CO—, C 1-10 An alkylene group or a bond represented by the formula R 8 represents H or an organic group.

[0201] R 8 The organic group in R is preferably an alkyl group. 8 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0202] In the formula, A is the same or different in each occurrence and is -COOM, -SO3M, or -OSO3M (M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group. 7 may be the same or different. In general formula (1), A is one of the preferred embodiments -COOM.

[0203] R 7 The organic group in R is preferably an alkyl group. 7 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred are alkyl groups of the formula: The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li.

[0204] M is H, a metal atom, or NR 7 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0205] In the formula, Y may be the same or different in each occurrence and may be -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 a divalent linking group selected from the group consisting of CO—, or a bond, R 8 represents H or an organic group.

[0206] Y is a bond, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 A divalent linking group selected from the group consisting of -CO- is preferred, and a divalent linking group selected from the group consisting of a bond, -COO-, and -OCO- is more preferred.

[0207] R 8 The organic group in R is preferably an alkyl group. 8 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C 1-4 More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0208] In the formula, R 6 In each occurrence, R may be the same or different and represent an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms. 6 The organic group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.

[0209] R 6 The alkyl group of R may contain one or more groups selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms, but does not contain these groups at the terminal of the alkyl group. 6 The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0210] R 6 As for General formula:-R 10 -CO-R 11 a group represented by General formula:-R 10 -COO-R 11 a group represented by General formula:-R 11 a group represented by General formula:-R 10 -NR 8 CO-R 11 or a group represented by General formula:-R 10 -CONR 8 -R 11 a group represented by (In the formula, R 8 represents H or an organic group. 10 is an alkylene group, R 11 is preferably an alkyl group which may have a substituent. R 6 As the general formula: -R 10 -CO-R 11 A group represented by the following formula is more preferred.

[0211] R 8 The organic group in R is preferably an alkyl group. 8 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferably H or C1-4 More preferred is an alkyl group of the formula (I), and even more preferred is H.

[0212] R 10 The number of carbon atoms in the alkylene group of R is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. 10 The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0213] R 11 The number of carbon atoms in the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 6, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. 11 The alkyl group of R is preferably composed of only primary, secondary, and tertiary carbon atoms, and particularly preferably composed of only primary and secondary carbon atoms. 11 As the alkyl group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, and a methyl group is most preferred.

[0214] In general formula (1), R 2 and R 5 In one preferred embodiment, at least one of the above is a group represented by the general formula: -XA, where A is -COOM.

[0215] The surfactant (1) is preferably a compound represented by general formula (1-1), a compound represented by general formula (1-2), or a compound represented by general formula (1-3), and more preferably a compound represented by general formula (1-1) or a compound represented by general formula (1-2).

[0216] General formula (1-1): [ka] (In the formula, R 3 ~R 6, X, A and Y are as above.)

[0217] General formula (1-2): [ka] (In the formula, R 4 ~R 6 , X, A and Y are as above.)

[0218] General formula (1-3): [ka] (In the formula, R 2 , R 4 ~R 6 , X, A and Y are as above.)

[0219] Examples of the group represented by the general formula -XA include: -COOM, -R 12 COOM, -SO3M, -OSO3M, -R 12 SO3M, -R 12 OSO3M, -OCO-R 12 -COOM, -OCO-R 12 -SO3M, -OCO-R 12 -OSO3M -COO-R 12 -COOM, -COO-R 12 -SO3M, -COO-R 12 -OSO3M, -CONR 8 -R 12 -COOM, -CONR 8 -R 12 -SO3M, -CONR 8 -R 12 -OSO3M, -NR 8 CO-R 12-COOM, -NR 8 CO-R 12 -SO3M, -NR 8 CO-R 12 -OSO3M, -OS(=O)2-R 12 -COOM, -OS(=O)2-R 12 -SO3M, or -OS(=O)2-R 12 -OSO3M (In the formula, R 8 and M are as above. 12 is C 1-10 An alkylene group represented by the formula: is preferred. Above R 12 In the alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0220] General formula:-YR 6 Examples of the group represented by the formula: General formula:-R 10 -CO-R 11 a group represented by General formula:-OCO-R 10 -CO-R 11 a group represented by General formula:-COO-R 10 -CO-R 11 a group represented by General formula:-OCO-R 10 -COO-R 11 a group represented by General formula:-COO-R 11 a group represented by General formula:-NR 8 CO-R 10 -CO-R 11 or a group represented by General formula:-CONR 8 -R 10 -NR 8CO-R 11 A group represented by (In the formula, R 8 , R 10 and R 11 is as described above.) is preferred.

[0221] In the formula, R 4 and R 5 are independently H or C 1-4 The alkyl groups are preferably: Above R 4 and R 5 The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0222] R in general formula (1-1) 3 is H or optionally substituted C 1-20 The alkyl group is preferably H or unsubstituted C 1-20 An alkyl group represented by the formula (I) is more preferred, and H is even more preferred. Above R 3 The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0223] R in general formula (1-3) 2 is H, OH or optionally substituted C 1-20 The alkyl group having no H, OH or substituent is preferably C 1-20 An alkyl group such as the above is more preferred, and H or OH is even more preferred. Above R 2The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0224] The hydrocarbon surfactant may be a surfactant represented by the following formula (1-0A): [ka] (In the formula, R 1A ~R 5A represents H, a monovalent hydrocarbon group which may contain an ester group between carbon atoms, or a group represented by the general formula: -X A -A, where R 2A and R 5A At least one of the groups has the general formula: -X A - represents a group represented by A. X A is, in each occurrence, the same or different, a divalent hydrocarbon radical or a bond; A is the same or different in each occurrence and is -COOM (M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group); R 1A ~R 5A Any two of these may be bonded to each other to form a ring.

[0225] In general formula (1-0A), R 1A ~R 5A In R, the monovalent hydrocarbon group which may contain an ester group between carbon atoms preferably has 1 to 50 carbon atoms, and more preferably has 5 to 20 carbon atoms. 1A ~R 5AAny two of these may be bonded to each other to form a ring. The monovalent hydrocarbon group which may contain an ester group between carbon atoms is preferably an alkyl group. In the formula, X A In the formula, the number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 50, and more preferably 5 to 20. Examples of the divalent hydrocarbon group include an alkylene group and an alkanediyl group, with an alkylene group being preferred.

[0226] In general formula (1-0A), R 2A and R 5A any one of the above general formula: -X A -A is preferred, and R 2A is represented by the above general formula: -X A A group represented by -A is more preferred.

[0227] In the general formula (1-0A), a preferred embodiment is R 2A is represented by the general formula: -X A -A, and R 1A , R 3A , R 4A and R 5A is H. In this case, X A is preferably a bond or an alkylene group having 1 to 5 carbon atoms.

[0228] In the general formula (1-0A), a preferred embodiment is also R 2A is represented by the general formula: -X A -A, and R 1A and R 3A Ga-Y A -R 6 and Y A is the same or different in each occurrence and is -COO-, -OCO-, or a bond; R 6 are the same or different in each occurrence and are alkyl groups having 2 or more carbon atoms. In this case, R 4A and R 5A is preferably H.

[0229] Examples of hydrocarbon surfactants represented by general formula (1-0A) include glutaric acid or a salt thereof, adipic acid or a salt thereof, pimelic acid or a salt thereof, suberic acid or a salt thereof, azelaic acid or a salt thereof, and sebacic acid or a salt thereof. Furthermore, the aliphatic carboxylic acid hydrocarbon surfactant represented by general formula (1-0A) may be a two-chain two-hydrophilic group synthetic surfactant, and examples of such Gemini surfactants include Geminisurf (Chukyo Yushi Co., Ltd.), Gemsurf α142 (12 carbon atoms, lauryl group), Gemsurf α102 (10 carbon atoms), and Gemsurf α182 (14 carbon atoms).

[0230] The hydrocarbon surfactant also includes a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). Furthermore, hydrocarbon surfactants obtained by subjecting the above hydrocarbon surfactants having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) to radical treatment or oxidation treatment can also be used. The radical treatment may be any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). For example, it involves adding deionized water and a hydrocarbon surfactant to a reactor, sealing the reactor, replacing the atmosphere with nitrogen, and then heating and pressurizing the reactor. Then, a polymerization initiator is added, the mixture is stirred for a certain period of time, and the pressure in the reactor is reduced to atmospheric pressure, followed by cooling. The oxidation treatment involves adding an oxidizing agent to a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). Examples of oxidizing agents include oxygen, ozone, hydrogen peroxide, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, and sulfur dioxide.

[0231] The hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) is preferably a surfactant represented by the formula: R X -X X (In the formula, R Xis a fluorine-free organic group having 1 to 2000 carbon atoms and one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), and X X -OSO3X X1 , -COOX X1 or -SO3X X1 (X X1 is H, metal atom, NR X1 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R X1 R is H or an organic group and may be the same or different. Surfactants represented by the formula: X R preferably has 500 or less carbon atoms, more preferably 100 or less, even more preferably 50 or less, and even more preferably 30 or less. X1 The organic group in R is preferably an alkyl group. X1 is 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. The hydrocarbon surfactant may be a surfactant represented by the following formula (a): [ka] (In the formula, R 1a R is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond, and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2a and R 3a R is independently a single bond or a divalent linking group. 1a , R 2a and R 3a X has a total of 6 or more carbon atoms. a is H, metal atom, NR 4a 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R4a are H or organic groups, and may be the same or different. 1a , R 2a and R 3a Any two of these may be bonded to each other to form a ring.) A surfactant (a) represented by the following formula (b): [ka] (In the formula, R 1b R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2b and R 4b are independently H or a substituent. 3b is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. X b is H, metal atom, NR 5b 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5b are H or organic groups, and may be the same or different. 1b , R 2b , R 3b and R 4b Any two of may 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- (However, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b represents H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents -OSO3X in the formula. b (b) a surfactant represented by the following formula (c): [ka] (In the formula, R 1c R is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond, and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2c and R 3c R is independently a single bond or a divalent linking group. 1c , R 2c and R 3c A has a total of 5 or more carbon atoms. c -COOX c or -SO3X c (X c is H, metal atom, NR 4c 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4c are H or organic groups, and may be the same or different. 1c , R 2c and R 3c Any two of these may be bonded to each other to form a ring.) and a surfactant (c) represented by the following formula (d): [ka] (In the formula, R 1d R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2d and R 4d are independently H or a substituent. 3d is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. A d -SO3X d or -COOXd (X d is H, metal atom, NR 5d 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5d are H or organic groups, and may be the same or different. 1d , R 2d , R 3d and R 4d Any two of may 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- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents A in the formula. d It is more preferable that the surfactant (d) is at least one selected from the group consisting of surfactants (d) represented by the formula:

[0232] The surfactant (a) will now be described.

[0233] 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. When the alkyl group has three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. In other words, acyl groups such as an acetyl group represented by CH3-C(=O)- are also included in the alkyl group. Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1a In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0234] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocycle. For example, a group represented by CH3-C(=O)-CH2- has 3 carbon atoms, a group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and a group represented by CH3-C(=O)- has 2 carbon atoms.

[0235] In the alkyl group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkyl group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 101a (In the formula, R 101a is an alkyl group). The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0236] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group. R 2a and R 3aare preferably independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms. R 2a and R 3a The alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0237] In the alkylene group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkylene group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 102a (In the formula, R 102a is an alkyl group). The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0238] R 1a , R 2a and R 3a has a total carbon number of 6 or more. The total carbon number is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. R 1a , R 2a and R 3a Any two of these may be bonded to each other to form a ring.

[0239] In formula (a), X a is H, metal atom, NR 4a 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4a is H or an organic group.4a may be the same or different. 4a The organic group in R is preferably an alkyl group. 4a is 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. X a H, alkali metals (group 1), alkaline earth metals (group 2) or NR 4a X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. a When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the PTFE or the final product.

[0240] R 1a As the alkyl group, 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 containing a monovalent or divalent heterocycle having 3 to 45 carbon atoms is preferred.

[0241] Also, R 1a As the formula: [ka] (In the formula, n 11a is an integer between 0 and 10, and R 11a is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R 12a is an alkylene group having 0 to 3 carbon atoms. 11a is an integer between 2 and 10, R 12amay be the same or different. ) is more preferred.

[0242] n 11a is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably an integer of 1 to 3.

[0243] R 11a The alkyl group as above preferably does not contain a carbonyl group. R 11a In the alkyl group as above, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkyl group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 103a (In the formula, R 103a is an alkyl group). R 11a The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0244] R 12a is an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3. R 12a The alkylene group as may be linear or branched. R 12a The alkylene group as R preferably does not contain a carbonyl group. 12a As the alkyl group, an ethylene group (-C2H4-) or a propylene group (-C3H6-) is more preferred. R 12aIn the alkylene group as above, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkylene group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 104a (In the formula, R 104a is an alkyl group). R 12a The alkylene group as above may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0245] R 2a and R 3a are each independently preferably an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0246] Examples of surfactant (a) include the following surfactants: a is as described above.

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] [ka]

[0253] [ka]

[0254] [ka]

[0255] The surfactant (a) is a novel compound and can be produced, for example, by the production method exemplified below.

[0256] The surfactant (a) has the formula: [ka] (In the formula, R 3a As mentioned above, E a is a leaving group.) and lithium and a compound (10a) represented by the formula: R 201a 3Si-Cl (wherein, R 201a are independently an alkyl group or an aryl group. [ka] (In the formula, R 3a , R 201a and E a is as described above.), Compound (11a) and a compound of formula: [ka] (In the formula, R 1a As mentioned above, R 21a is a single bond or a divalent linking group.) to form an olefin represented by the formula: [ka] (In the formula, R 1a , R 21a , R 3a and E a is as described above.), The leaving group of compound (12a) is removed to give a compound of the formula: [ka] (In the formula, R 1a , R 21a and R 3a is as described above.) and Compound (13a) and a compound of formula: [ka] (In the formula, X a is as described above.) to give a sulfonic acid chloride represented by the formula: [ka] (In the formula, R 1a , R 21a , R 3a and X a The compound (14a) can be produced by a production method including a step (14a) of obtaining a compound (14a) represented by the formula (14a) as described above.

[0257] R 1a When the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0258] In step (11a), it is preferable to first react lithium with the chlorosilane compound to obtain a siloxylithium compound, and then react the siloxylithium compound with compound (10a) to obtain compound (11a).

[0259] E a represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, and a benzyl (Bn) group.

[0260] R 21a is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0261] Examples of the chlorosilane compound include: [ka] Examples include:

[0262] Any reaction in step (11a) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether. 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Among these, tetrahydrofuran and diethyl ether are preferred.

[0263] The temperature for the reaction of lithium with the chlorosilane compound in step (11a) is preferably 10 to 40°C, more preferably 20 to 30°C. The temperature for the reaction of the siloxylithium compound with the compound (10a) in the step (11a) is preferably from -100 to 0°C, more preferably from -80 to -50°C.

[0264] The pressure for the reaction of lithium with the chlorosilane compound in step (11a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa. The pressure for the reaction of the siloxylithium compound with the compound (10a) in the step (11a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0265] The reaction time of lithium and the chlorosilane compound in step (11a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours. The reaction time of the siloxylithium compound with the compound (10a) in the step (11a) is preferably 0.1 to 72 hours, more preferably 1 to 2 hours.

[0266] In the step (12a), the reaction ratio of compound (11a) and the olefin is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the olefin per mole of compound (11a), in consideration of improving the yield and reducing waste.

[0267] The reaction in step (12a) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0268] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

[0269] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0270] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0271] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0272] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0273] The reaction temperature in step (12a) is preferably 40 to 60°C, more preferably 50 to 55°C.

[0274] The reaction pressure in step (12a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0275] The reaction time in step (12a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0276] The elimination reaction of the leaving group in step (13a) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include 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 borofluoride (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0277] The elimination reaction of the leaving group in step (13a) can be carried out in a solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0278] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0279] The reaction temperature in step (13a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0280] The reaction pressure in step (13a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0281] The reaction time in step (13a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0282] In the step (14a), the reaction ratio of compound (13a) and the sulfonic chloride is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the sulfonic chloride relative to 1 mole of compound (13a), in consideration of improving the yield and reducing waste.

[0283] The reaction in step (14a) is preferably carried out in the presence of a base, such as an alkali metal hydroxide, an alkaline earth metal hydroxide, or an amine, with an amine being preferred.

[0284] Examples of the amine in step (14a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, and N,N,N',N'-tetramethyl-1,8-naphthalenediamine; heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, and lutidine; and cyclic amines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and 1,5-diaza-bicyclo[4.3.0]-5-nonene. Of these, triethylamine and pyridine are preferred.

[0285] The amount of the base used in step (14a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, per mole of compound (13a), in consideration of improving yield and reducing waste.

[0286] The reaction in step (14a) can be carried out in a polar solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0287] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6), and among these, diethyl ether is preferred.

[0288] The reaction temperature in step (14a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0289] The reaction pressure in step (14a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0290] The reaction time in step (14a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0291] When the reaction in step (14a) is carried out in a solvent, a solution containing compound (14a) is obtained after completion of the reaction. After adding water to the solution, the mixture is allowed to stand to separate into two phases, and the aqueous phase is recovered. High-purity compound (14a) can be recovered by distilling off the solvent. When compound (14a) has a group represented by -OSOH (i.e., when X is H), -OSOH can be converted to a sulfate group by using an aqueous alkali solution such as aqueous sodium bicarbonate or aqueous ammonia instead of water.

[0292] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0293] The surfactant (a) may also be a compound represented by the formula: [ka] (In the formula, R 3a As mentioned above, R 22a is a monovalent organic group, E a is a leaving group.) and a ketone represented by the formula: [ka] (In the formula, R 1a As mentioned above, R 23a is a monovalent organic group.) to react with a carboxylic acid ester represented by the formula: [ka] (In the formula, R 1a , R 3a and E a As mentioned above, R 24a is a single bond or a divalent linking group.), The leaving group of compound (21a) is removed to give a compound of the formula: [ka] (In the formula, R 1a , R24a and R 3a is as described above.) and Compound (22a) and a compound of formula: [ka] (In the formula, X a is as described above.) to give a sulfonic acid chloride represented by the formula: [ka] (In the formula, R 1a , R 24a , R 3a and X a is as described above.)

[0294] R 1a When the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0295] E a represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, and a benzyl (Bn) group.

[0296] R 22a As the alkyl group, a linear or branched alkyl group having one or more carbon atoms is preferred, and a methyl group is more preferred. R 23a As the alkyl group, a linear or branched alkyl group having one or more carbon atoms is preferred, and a methyl group is more preferred. R 24a As the alkyl group, a linear or branched alkylene group having one or more carbon atoms is preferred, and a methylene group (—CH2—) is more preferred.

[0297] The reaction in step (21a) can be carried out in a solvent in the presence of a base.

[0298] Examples of the base include sodium amide, sodium hydride, sodium methoxide, and sodium ethoxide.

[0299] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0300] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0301] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0302] The reaction temperature in step (21a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0303] The reaction pressure in the step (21a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0304] The reaction time in step (21a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0305] The elimination reaction of the leaving group in step (22a) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include 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 borofluoride (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0306] The elimination reaction of the leaving group in step (22a) can be carried out in a solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0307] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0308] The reaction temperature in step (22a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0309] The reaction pressure in the step (22a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0310] The reaction time in step (22a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0311] In the step (23a), the reaction ratio of compound (22a) and the sulfonic chloride is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the sulfonic chloride relative to 1 mole of compound (22a), in consideration of improving the yield and reducing waste.

[0312] The reaction in step (23a) is preferably carried out in the presence of a base, such as an alkali metal hydroxide, an alkaline earth metal hydroxide, or an amine, with an amine being preferred.

[0313] Examples of the amine in step (23a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, and N,N,N',N'-tetramethyl-1,8-naphthalenediamine; heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, and lutidine; and cyclic amines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and 1,5-diaza-bicyclo[4.3.0]-5-nonene. Of these, triethylamine and pyridine are preferred.

[0314] The amount of the base used in step (23a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, per mole of compound (22a), in consideration of improving yield and reducing waste.

[0315] The reaction in step (23a) can be carried out in a polar solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0316] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6), and among these, diethyl ether is preferred.

[0317] The reaction temperature in step (23a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0318] The reaction pressure in the step (23a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0319] The reaction time in step (23a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0320] When the reaction in step (23a) is carried out in a solvent, a solution containing compound (23a) is obtained after completion of the reaction. After adding water to the solution, the mixture is allowed to stand to separate into two phases, and the aqueous phase is recovered. High-purity compound (23a) can be recovered by distilling off the solvent. When compound (23a) has a group represented by -OSOH (i.e., when X is H), -OSOH can be converted to a sulfate group by using an alkaline aqueous solution such as aqueous sodium bicarbonate or aqueous ammonia instead of water.

[0321] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0322] The surfactant (a) may also be a compound represented by the formula: Y a -R 3a -OE a (In the formula, R 3a As mentioned above, Y a is a halogen atom, E ais a leaving group.) and an alkyl halide of the formula: [ka] (In the formula, R 1a is as described above.) to form a compound represented by the formula: [ka] (In the formula, R 1a , R 3a and E a is as described above.), and a step (31a) of obtaining a compound (31a) represented by the formula [ka] (In the formula, R 1a , R 3a and E a is as described above.) to obtain a compound (32a) represented by the formula (32a), The leaving group of compound (32a) is removed to give a compound of the formula: [ka] (In the formula, R 1a and R 3a is as described above.) to obtain a compound (33a) represented by the formula (33a), and Compound (33a) and a compound of formula: [ka] (In the formula, X a is as described above.) to give a sulfonic acid chloride represented by the formula: [ka] (In the formula, R 1a , R 3a and X a The compound (34a) can be produced by a production method including a step (34a) of obtaining a compound (34a) represented by the formula (34a) as described above.

[0323] R 1a When the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0324] E a represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, and a benzyl (Bn) group.

[0325] In the step (31a), the reaction ratio of the alkyl halide to the lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles, of the lithium acetylide per mole of the alkyl halide, in consideration of improving yield and reducing waste.

[0326] The reaction in step (31a) can be carried out in a solvent, preferably hexane.

[0327] The reaction temperature in step (31a) is preferably from -100 to -40°C, more preferably from -80 to -50°C.

[0328] The reaction pressure in the step (31a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0329] The reaction time in step (31a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0330] The oxidation in step (32a) is carried out by reacting [(Cn * )Ru III (CF3CO2)3]·H2O (wherein, Cn *This can be carried out in a nitrile solvent using the complex formed by treating 1,4,7-trimethyl-1,4,7-triazabicyclononane (wherein 1,4,7-trimethyl-1,4,7-triazabicyclononane) with (NH4)2Ce(NO3)6 and trifluoroacetic acid, followed by the addition of sodium perchlorate.

[0331] After the oxidation is complete, the reaction mixture may be neutralized with an alkali, and compound (32a) may be extracted using an organic solvent such as ether.

[0332] The reaction temperature in step (32a) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0333] The reaction pressure in the step (32a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0334] The reaction time in step (32a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0335] The elimination reaction of the leaving group in step (33a) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include 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 borofluoride (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0336] The elimination reaction of the leaving group in step (33a) can be carried out in a solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0337] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0338] The reaction temperature in step (33a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0339] The reaction pressure in the step (33a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0340] The reaction time in step (33a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0341] In the step (34a), the reaction ratio of compound (33a) and the sulfonic chloride is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the sulfonic chloride relative to 1 mole of compound (33a), in consideration of improving the yield and reducing waste.

[0342] The reaction in step (34a) is preferably carried out in the presence of a base, such as an alkali metal hydroxide, an alkaline earth metal hydroxide, or an amine, with an amine being preferred.

[0343] Examples of the amine in step (34a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, and N,N,N',N'-tetramethyl-1,8-naphthalenediamine; heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, and lutidine; and cyclic amines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and 1,5-diaza-bicyclo[4.3.0]-5-nonene. Of these, triethylamine and pyridine are preferred.

[0344] The amount of the base used in step (34a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, per mole of compound (33a), in consideration of improving yield and reducing waste.

[0345] The reaction in step (34a) can be carried out in a polar solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0346] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6), and among these, diethyl ether is preferred.

[0347] The reaction temperature in step (34a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0348] The reaction pressure in the step (34a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0349] The reaction time in step (34a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0350] When the reaction in step (34a) is carried out in a solvent, a solution containing compound (34a) is obtained after completion of the reaction. After adding water to the solution, the mixture is allowed to stand to separate into two phases, and the aqueous phase is recovered. High-purity compound (34a) can be recovered by distilling off the solvent. When compound (34a) has a group represented by —OSOH (i.e., when X is H), —OSOH can be converted to a sulfate group by using an aqueous alkali solution such as aqueous sodium bicarbonate or aqueous ammonia instead of water.

[0351] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0352] The surfactant (a) may also be a compound represented by the formula: [ka] (In the formula, R 1a As mentioned above, R 21a is a single bond or a divalent linking group.) and an alkene represented by the formula: [ka] (In the formula, Y 51a is an alkoxyl group.) to give an alkyne represented by the formula: [ka] (In the formula, R 1a and R 21a is as described above.) Step (41a) of obtaining a compound (41a) represented by Compound (41a) is a compound of the formula: [ka] (In the formula, X a is as described above.) to give a sulfonic acid chloride represented by the formula: [ka] (In the formula, R 1a , R 21a and X a is as described above.)

[0353] R 1a When the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0354] R 21a is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0355] In the step (41a), the reaction ratio of the alkene to the alkyne is preferably 0.5 to 2 moles, more preferably 0.6 to 1.2 moles, of the alkene per mole of the alkyne, in consideration of improving the yield and reducing waste products.

[0356] The reaction in step (41a) is preferably carried out in the presence of a metal catalyst, such as ruthenium.

[0357] The amount of the metal catalyst used in step (41a) is preferably 0.01 to 0.4 mol, more preferably 0.05 to 0.1 mol, per 1 mol of the alkene, in consideration of improving yield and reducing waste.

[0358] The reaction in step (41a) can be carried out in a polar solvent, preferably water, acetonitrile, dimethylacetamide, or dimethylformamide.

[0359] The reaction temperature in step (41a) is preferably 20 to 160°C, more preferably 40 to 140°C.

[0360] The reaction pressure in the step (41a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0361] The reaction time in step (41a) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0362] In the step (42a), the reaction ratio of compound (41a) and the sulfonic chloride is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the sulfonic chloride relative to 1 mole of compound (41a), in consideration of improving the yield and reducing waste.

[0363] The reaction in step (42a) is preferably carried out in the presence of a base, such as an alkali metal hydroxide, an alkaline earth metal hydroxide, or an amine, with an amine being preferred.

[0364] Examples of the amine in step (42a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine, and N,N,N',N'-tetramethyl-1,8-naphthalenediamine; heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, and lutidine; and cyclic amines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and 1,5-diaza-bicyclo[4.3.0]-5-nonene. Of these, triethylamine and pyridine are preferred.

[0365] The amount of the base used in step (42a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, per mole of compound (41a), in consideration of improving the yield and reducing waste.

[0366] The reaction in step (42a) can be carried out in a polar solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0367] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6), and among these, diethyl ether is preferred.

[0368] The reaction temperature in step (42a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0369] The reaction pressure in the step (42a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0370] The reaction time in step (42a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0371] When the reaction in step (42a) is carried out in a solvent, a solution containing compound (42a) is obtained after completion of the reaction. After adding water to the solution, the mixture is allowed to stand to separate into two phases, and the aqueous phase is recovered. High-purity compound (42a) can be recovered by distilling off the solvent. When compound (42a) has a group represented by —OSOH (i.e., when X is H), —OSOH can be converted to a sulfate group by using an aqueous alkali solution such as aqueous sodium bicarbonate or aqueous ammonia instead of water.

[0372] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0373] Next, the surfactant (b) will be described.

[0374] In formula (b), R 1bis a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1b In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0375] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0376] R 1b The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0377] R 1b The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0378] R 1bAs the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0379] In formula (b), R 2b and R 4b are independently H or a substituent. 2b and R 4b may be the same or different.

[0380] R 2b and R 4b The substituent as is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0381] R 2b and R 4b The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0382] R 2b and R 4bThe alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0383] R 2b and R 4b are each independently preferably H or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not containing a substituent, even more preferably H, a methyl group (-CH3), or an ethyl group (-C2H5), and particularly preferably H.

[0384] In formula (b), R 3b R is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3b When there are a plurality of, they may be the same or different.

[0385] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0386] The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, 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 have a substituent, and still more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0387] R 1b , R 2b , R 3b and R 4b Any two of may be bonded to each other to form a ring, but it is preferable that they do not form a ring.

[0388] In formula (b), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, still more preferably an integer of 5 to 25, and particularly preferably an integer of 5 to 9 or 11 to 25.

[0389] In formula (b), p and q are independently an integer of 0 or greater. 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.

[0390] The sum of n, p, and q is preferably an integer of 5 or greater. The sum of n, p, and q is more preferably an integer of 8 or greater. 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 even more preferably an integer of 40 or less.

[0391] In formula (b), X b is H, metal atom, NR 5b 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5bis H or an organic group. 5b may be the same or different. 5b The organic group in R is preferably an alkyl group. 5b is 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred. X b is a metal atom or NR 5b 4(R 5b is as above). X b H, alkali metals (group 1), alkaline earth metals (group 2) or NR 5b X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. b When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the PTFE or the final product.

[0392] In formula (b), L represents a single bond, -CO2-B-*, -OCO-B-*, or -CONR 6b -B-*, -NR 6b CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group more preferably has 1 to 5 carbon atoms. 6 is more preferably H or a methyl group. * represents -OSO3X in the formula. b This refers to the side that binds to the

[0393] L is preferably a single bond.

[0394] The surfactant (b) may be a compound represented by the following formula: [ka] (In the formula, R 1b , R 2b , L, n and X b is as described above. ) is preferred.

[0395] The surfactant (b) is 1 In the 1 H-NMR spectrum, the integral value of all peak intensities observed in the chemical shift region of 2.0 to 5.0 ppm is preferably 10% or more.

[0396] The surfactant (b) is 1 In the H-NMR spectrum, the integrated value of all peak intensities observed in the chemical shift region of 2.0 to 5.0 ppm is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0397] In the surfactant (b), the integral value is more preferably 15 or more, and is preferably 95 or less, more preferably 80 or less, and even more preferably 70 or less.

[0398] The above integral value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

[0399] Examples of the surfactant (b) include: CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2OSO3Na、 (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na、 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na、 CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, Examples include CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na.

[0400] The surfactant (b) is a novel compound and can be produced, for example, by the production method exemplified below.

[0401] The surfactant (b) is represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH (In the formula, R 2b ~R 4b , n, p and q are as above. R 11b is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6bCO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6b The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side bonded to —OH in the formula.) is hydroxylated to obtain a compound (10b) represented by the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 11b , n, p and q are as defined above.), Compound (11b) is oxidized to give the compound of the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 11b , n, p and q are as defined above.), and Compound (12b) is converted into a sulfate ester to obtain a compound of the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 11b , n, p, q and X b can be produced by a production method including a step (13b) of obtaining a compound (13b) represented by the formula (13b) as described above.

[0402] R 11b The alkyl group as above preferably does not contain a carbonyl group. R 11bThe alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0403] R 11b is preferably H, a linear or branched alkyl group of 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group of 3 to 9 carbon atoms which may have a substituent; more preferably H, a linear or branched alkyl group of 1 to 9 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group of 3 to 9 carbon atoms which does not contain a carbonyl group; even more preferably H, or a linear or branched alkyl group of 1 to 9 carbon atoms which does not have a substituent; even more preferably H, a methyl group (-CH3), or an ethyl group (-C2H5); particularly preferably H or a methyl group (-CH3), and most preferably H.

[0404] The hydroxylation in step (11b) can be carried out, for example, by (1) reacting compound (10b) with phthalocyanine iron (II) (Fe(Pc)) and sodium borohydride in an oxygen atmosphere, or (2) reacting compound (10b) with isopinocampheylborane (IpcBH) and then oxidizing the resulting intermediate (dialkylborane).

[0405] In the method (1), the amount of phthalocyanine iron(II) may be a catalytic amount, and it can be used in an amount of 0.001 to 1.2 moles per mole of compound (10b).

[0406] In the method (1), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (10b).

[0407] The reaction of the method (1) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, an aromatic hydrocarbon, a nitrile, or a nitrogen-containing polar organic compound.

[0408] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0409] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0410] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0411] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0412] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0413] The reaction temperature in the method (1) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0414] The reaction pressure in the method (1) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0415] The reaction time in the method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0416] In the method (2), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per mole of compound (10b).

[0417] The reaction of compound (10b) with isopinocampheylborane can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0418] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0419] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0420] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0421] The temperature for the reaction of compound (10b) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0422] The pressure for the reaction of compound (10b) with isopinocampheylborane is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0423] The reaction time of compound (10b) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0424] The oxidation in method (2) can be carried out by reacting the intermediate with an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide. The oxidizing agent can be used in an amount of 0.7 to 10 moles per mole of the intermediate.

[0425] The oxidation in method (2) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0426] The oxidation temperature in the method (2) is preferably 0 to 100°C, more preferably 0 to 80°C.

[0427] The oxidation pressure in the method (2) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0428] The oxidation time in method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0429] In step (12b), examples of methods 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 using a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as NiCl2, and (e) a method using a hydrogen acceptor such as an aldehyde or ketone in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0430] The oxidation in step (12b) can be carried out in a solvent, preferably water or an organic solvent, such as water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

[0431] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0432] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0433] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0434] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0435] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0436] The oxidation temperature in step (12b) is preferably from −78 to 200° C., and can be appropriately selected depending on the method employed.

[0437] The oxidation pressure in the step (12b) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0438] The oxidation time in step (12b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0439] The sulfation in step (13b) can be carried out by reacting compound (12b) with a sulfating reagent. Examples of the sulfating reagent include sulfur trioxide amine complexes such as sulfur trioxide pyridine complex, sulfur trioxide trimethylamine complex, and sulfur trioxide triethylamine complex; sulfur trioxide amide complexes such as sulfur trioxide dimethylformamide complex; sulfuric acid-dicyclohexylcarbodiimide; chlorosulfuric acid; concentrated sulfuric acid; and sulfamic acid. The amount of the sulfating reagent used is preferably 0.5 to 10 mol, more preferably 0.5 to 5 mol, and even more preferably 0.7 to 4 mol, per 1 mol of compound (12b).

[0440] The sulfonation in step (13b) can be carried out in a solvent, preferably an organic solvent, such as ether, halogenated hydrocarbon, aromatic hydrocarbon, pyridine, dimethyl sulfoxide, sulfolane, or nitrile.

[0441] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0442] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0443] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0444] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0445] The temperature for sulfonation in step (13b) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0446] The pressure for sulfonation in step (13b) is preferably 0 to 10 MPa, more preferably 0.1 to 5 MPa.

[0447] The time for sulfate esterification in step (13b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0448] The surfactant (b) may also be a compound represented by the following formula: [ka] (In the formula, L, R 1b ~R 4b , n, p and q are as above. R 101b is an organic group.) is subjected to ozonolysis to obtain a compound (20b) represented by the following formula: [ka] (In the formula, L, R 1b ~R 4b , n, p and q are as defined above.), and The compound (21b) is converted into a sulfate ester to obtain a compound of the following formula: [ka] (In the formula, L, R 1b ~R 4b , n, p, q and X b can be produced by a production method including a step (22b) of obtaining a compound (22b) represented by the formula (22b) as described above.

[0449] R 101b is preferably an alkyl group having 1 to 20 carbon atoms. 101b may be the same or different.

[0450] The ozonolysis in step (21b) can be carried out by reacting compound (20b) with ozone, followed by post-treatment with a reducing agent.

[0451] Ozone can be generated by silent electrical discharge in oxygen gas.

[0452] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0453] The ozonolysis in step (21b) can be carried out in a solvent, preferably water or an organic solvent, such as water, alcohol, carboxylic acids, ethers, halogenated hydrocarbons, and aromatic hydrocarbons.

[0454] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0455] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0456] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0457] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0458] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0459] The temperature for ozonolysis in step (21b) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0460] The pressure for ozonolysis in the step (21b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0461] The time for ozonolysis in step (21b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0462] The sulfate esterification in step (22b) can be carried out by reacting compound (21b) with a sulfating reagent, and the same conditions as those for the sulfate esterification in step (13b) can be used.

[0463] The surfactant (b) may also be a compound represented by the following formula: R 21b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH (In the formula, L, R 2b ~R 4b , n, p and q are as above. R 21b is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring, to thereby obtain a compound (30b) represented by the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 21b , n, p and q are as defined above.), Compound (31b) and R 22b 2CuLi(R 22b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring.) to react with a dialkyl copper lithium represented by the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 21b , R 22b , n, p and q are as defined above.), Compound (32b) is oxidized to give the compound of the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 21b , R 22b , n, p and q are as defined above.), and The compound (33b) is converted into a sulfate ester to obtain a compound of the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 21b , R 22b , n, p, q and X b can be produced by a production method including a step (34b) of obtaining a compound (34b) represented by the formula (34b) as described above.

[0464] R 21b The alkyl group as above preferably does not contain a carbonyl group. R 21b The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0465] R 21bis preferably H, a linear or branched alkyl group of 1 to 8 carbon atoms which may have a substituent, or a cyclic alkyl group of 3 to 8 carbon atoms which may have a substituent; more preferably H, a linear or branched alkyl group of 1 to 8 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group of 3 to 8 carbon atoms which does not contain a carbonyl group; still more preferably H, or a linear or branched alkyl group of 1 to 8 carbon atoms which does not have a substituent; particularly preferably H or a methyl group (—CH3), and most preferably H.

[0466] R 22b The alkyl group as above preferably does not contain a carbonyl group. R 22b The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0467] R 22b As the alkyl group, a linear or branched alkyl group having 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms which may have a substituent, is preferred, a linear or branched alkyl group having 1 to 9 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 9 carbon atoms which does not have a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0468] 2 R's 22b may be the same or different.

[0469] R 21b and R 22bPreferably, the total number of carbon atoms is 1 to 7, more preferably 1 or 2, and most preferably 1.

[0470] The epoxidation in step (31b) can be carried out by reacting compound (30b) with an epoxidizing agent.

[0471] Examples of the epoxidizing agent include metachloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, peracids such as tert-butyl hydroperoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, etc., and among these, peracids are preferred, with metachloroperbenzoic acid being more preferred. The epoxidizing agent can be used in an amount of 0.5 to 10.0 moles per mole of compound (30b).

[0472] The epoxidation in step (31b) can be carried out in a solvent, preferably an organic solvent such as ketone, ether, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, pyridine, nitrogen-containing polar organic compound, dimethyl sulfoxide, etc., with dichloromethane being particularly preferred.

[0473] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0474] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0475] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0476] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0477] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0478] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0479] The epoxidation temperature in step (31b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0480] The pressure for epoxidation in step (31b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0481] The epoxidation time in step (31b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0482] In the step (32b), the dialkyl copper lithium can be used in an amount of 0.5 to 10.0 moles per mole of the compound (31b).

[0483] The reaction in step (32b) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0484] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0485] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0486] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0487] The reaction temperature in step (32b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0488] The reaction pressure in step (32b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0489] The reaction time in step (32b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0490] In step (33b), examples of methods for oxidizing compound (32b) 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 (a 5-6% aqueous solution of NaOCl) is reacted in the presence of a nickel compound such as NiCl2, and (e) a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0491] The oxidation in step (33b) can be carried out in a solvent, preferably water or an organic solvent, such as water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

[0492] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0493] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0494] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0495] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0496] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0497] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0498] The oxidation temperature in the step (33b) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0499] The oxidation pressure in the step (33b) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0500] The oxidation time in step (33b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0501] The sulfate esterification in step (34b) can be carried out by reacting compound (33b) with a sulfating reagent, and the same conditions as those for the sulfate esterification in step (13b) can be used.

[0502] The surfactant (b) may also be a compound represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -(OR 3b ) p -(CR 4b 2) q -L-OH (In the formula, L, R 2b ~R 4b , R 11b , n, p and q are as defined above.) to obtain a compound (10b) represented by the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 11b , n, p and q are as defined above.), and The compound (41b) is converted into a sulfate ester to obtain a compound of the following formula: [ka] (In the formula, L, R 2b ~R 4b , R 11b , n, p, q and X b can be produced by a production method including a step (42b) of obtaining a compound (42b) represented by the formula (42b) as described above.

[0503] The oxidation in step (41b) can be carried out by reacting compound (10b) with an oxidizing agent in the presence of water and a palladium compound.

[0504] Examples of the oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide, copper trifluoromethanethiol, etc., iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanethiol, iron hexacyano, etc., benzoquinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, etc., HO, MnO, KMnO, RuO, m-chloroperbenzoic acid, oxygen, etc. Among these, copper salts, iron salts, and benzoquinones are preferred, and copper chloride, iron chloride, and 1,4-benzoquinone are more preferred. The oxidizing agent can be used in an amount of 0.001 to 10 moles per mole of compound (10b).

[0505] The water can be used in an amount of 0.5 to 1000 moles per mole of compound (10b).

[0506] The palladium compound may be palladium dichloride, and the amount of the palladium compound may be a catalytic amount, and may be 0.0001 to 1.0 moles per mole of compound (10b).

[0507] The oxidation in step (41b) can be carried out in a solvent, such as water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, or sulfolane.

[0508] Examples of the ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and among these, ethyl acetate is preferred.

[0509] Examples of the aliphatic hydrocarbon include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc., and among these, cyclohexane and heptane are preferred.

[0510] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0511] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0512] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0513] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0514] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0515] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0516] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0517] The oxidation temperature in step (41b) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0518] The oxidation pressure in the step (41b) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0519] The oxidation time in step (41b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0520] The sulfate esterification in step (42b) can be carried out by reacting compound (41b) with a sulfating reagent, and the same conditions as those for the sulfate esterification in step (13b) can be used.

[0521] The surfactant (b) may also be a compound represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -OH (In the formula, R 2b , R 11b and n are as defined above.) is reacted with a halogenating agent to obtain a compound represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -Z 51b (In the formula, R 2b , R 11b and n is as above. Z 51b is a halogen atom), Compound (51) and HO-R 3b -L-OH(L, R 3b is as described above.) to react with an alkylene glycol represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -OR 3b -L-OH (In the formula, L, R 2b , R 3b , R 11b and n is as defined above.), Compound (52) is oxidized to give the compound of the following formula: [ka] (In the formula, L, R2b , R 3b , R 11b and n is as defined above.), and The compound (53) is converted into a sulfate ester to obtain a compound of the following formula: [ka] (In the formula, L, R 2b , R 3b , R 11b , n and X b can be produced by a production method including a step (54) of obtaining a compound (54) represented by the formula:

[0522] Z 51b is preferably F, Cl, Br or I, and more preferably Br.

[0523] Examples of the halogenating agent used in step (51) include N-bromosuccinimide and N-chlorosuccinimide. The halogenating agent can be used in an amount of 0.5 to 10.0 mol per 1 mol of compound (50).

[0524] The reaction in step (51) can be carried out in the presence of a phosphine such as triphenylphosphine. The phosphines can be used in an amount of 0.5 to 10.0 moles per mole of compound (50).

[0525] The reaction in step (51) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0526] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0527] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0528] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0529] The reaction temperature in step (51) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0530] The reaction pressure in step (51) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0531] The reaction time in step (51) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0532] In the step (52), the alkylene glycol can be used in an amount of 0.5 to 10.0 moles per mole of the compound (51).

[0533] The reaction in step (52) can be carried out in the presence of a base, such as sodium hydride, sodium hydroxide, or potassium hydroxide. The base can be used in an amount of 0.5 to 10.0 moles per mole of compound (51).

[0534] The reaction in step (52) can be carried out in a solvent, preferably an organic solvent, such as a nitrogen-containing polar organic compound, an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0535] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0536] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0537] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0538] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0539] The reaction temperature in step (52) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0540] The reaction pressure in step (52) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0541] The reaction time in step (52) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0542] The oxidation in step (53) can be carried out by reacting compound (52) with an oxidizing agent in the presence of water and a palladium compound, and the same conditions as those for the oxidation in step (41) can be used.

[0543] The sulfate esterification in step (54) can be carried out by reacting compound (53) with a sulfating reagent, and the same conditions as those for the sulfate esterification in step (13) can be used.

[0544] In any of the above-mentioned production methods, after completion of each step, the purity of the obtained compound may be increased by distilling off the solvent, or by carrying out distillation, purification, etc. In addition, when the obtained compound has a group represented by -OSO3H (i.e., X b When -OSO3H is H, it can be converted to a sulfate group by contact with an alkali such as sodium carbonate or ammonia.

[0545] Among the methods for producing the surfactant (b), a production method including the above steps (41b) and (42b) is preferred.

[0546] The surfactant (c) will now be explained.

[0547] 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. When the alkyl group has three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. In other words, acyl groups such as an acetyl group represented by CH3-C(=O)- are also included in the alkyl group. Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1c In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0548] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocycle. For example, a group represented by CH3-C(=O)-CH2- has 3 carbon atoms, a group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- has 7 carbon atoms, and a group represented by CH3-C(=O)- has 2 carbon atoms.

[0549] In the alkyl group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkyl group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 101c (In the formula, R 101c is an alkyl group). The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0550] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group. R 2c and R 3c are preferably independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms. R 2c and R 3c The alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0551] In the alkylene group, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, with a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkylene group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 102c (In the formula, R 102c is an alkyl group). The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0552] R 1c , R 2c and R 3c has a total carbon number of 5 or more. The total carbon number is preferably 7 or more, more preferably 9 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. R 1c , R 2c and R 3c Any two of these may be bonded to each other to form a ring.

[0553] In formula (c), in formula, A c -COOX c or -SO3X c (X c is H, metal atom, NR 4c 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4c are H or organic groups, and may be the same or different. 4c The organic group in R is preferably an alkyl group. 4cis 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. The metal atom includes monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K, or Li. X c H, alkali metals (group 1), alkaline earth metals (group 2) or NR 4c X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. c When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the PTFE or the final product.

[0554] R 1c As the alkyl group, 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 containing a monovalent or divalent heterocycle having 3 to 45 carbon atoms is preferred.

[0555] Also, R 1c As the formula: [ka] (In the formula, n 11c is an integer between 0 and 10, and 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. 11c is an integer between 2 and 10, R 12c may be the same or different. ) is more preferred.

[0556] n11c is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably an integer of 1 to 3.

[0557] R 11c The alkyl group as above preferably does not contain a carbonyl group. R 11c In the alkyl group as above, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkyl group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 103c (In the formula, R 103c is an alkyl group). R 11c The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0558] R 12c is an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3. R 12c The alkylene group as may be linear or branched. R 12c The alkylene group as R preferably does not contain a carbonyl group. 12c As the alkyl group, an ethylene group (-C2H4-) or a propylene group (-C3H6-) is more preferred. R 12c In the alkylene group as above, a hydrogen atom bonded to a carbon atom may be substituted with a functional group, for example, a hydroxy group (—OH) or a monovalent organic group containing an ester bond, but it is preferable that the alkylene group is not substituted with any functional group. The monovalent organic group containing an ester bond is a group represented by the formula: -OC(=O)-R 104c (In the formula, R 104c is an alkyl group). R 12c The alkylene group as above may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0559] R 2c and R 3c are each independently preferably an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0560] Examples of the surfactant (c) include the following surfactants: c is as described above.

[0561] [ka]

[0562] [ka]

[0563] [ka]

[0564] [ka]

[0565] [ka]

[0566] [ka]

[0567] [ka]

[0568] [ka]

[0569] The surfactant (c) is a novel compound and can be produced, for example, by the production method exemplified below.

[0570] The surfactant (c) has the formula: [ka] (In the formula, R 3c As mentioned above, E c is a leaving group.) and lithium and a compound (10c) represented by the formula: R 201c 3Si-Cl (wherein, R 201c are independently an alkyl group or an aryl group. [ka] (In the formula, R 3c , R 201c and E c is as described above.), Compound (11c) and a compound of formula: [ka] (In the formula, R 1c As mentioned above, R 21c is a single bond or a divalent linking group.) to form an olefin represented by the formula: [ka] (In the formula, R 1c , R 21c , R 3c and E c is as described above.), The leaving group of compound (12c) is removed to give a compound of the formula: [ka] (In the formula, R 1c , R 21c and R 3c is as described above.) and Compound (13c) is oxidized to give a compound of the formula: [ka] (In the formula, R 1c , R 21c and R 3c as described above.) to obtain a compound (14c) represented by the formula (14c), It can be suitably produced by a production method including the steps of:

[0571] R 1c When the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0572] In step (11c), it is preferable to first react lithium with the chlorosilane compound to obtain a siloxylithium compound, and then react the siloxylithium compound with compound (10c) to obtain compound (11c).

[0573] E crepresents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, and a benzyl (Bn) group.

[0574] R 21c is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0575] Examples of the chlorosilane compound include: [ka] Examples include:

[0576] Any reaction in step (11c) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether. 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Among these, tetrahydrofuran and diethyl ether are preferred.

[0577] The temperature for the reaction of lithium with the chlorosilane compound in step (11c) is preferably from -78 to 100°C, more preferably from 10 to 40°C. The temperature for the reaction of the siloxylithium compound with the compound (10c) in the step (11c) is preferably from -100 to 0°C, more preferably from -80 to -50°C.

[0578] The pressure for the reaction of lithium with the chlorosilane compound in step (11c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa. The pressure for the reaction of the siloxylithium compound with the compound (10c) in the step (11c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0579] The reaction time of lithium and the chlorosilane compound in step (11c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours. The reaction time of the siloxylithium compound with the compound (10c) in the step (11c) is preferably 0.1 to 72 hours, more preferably 1 to 2 hours.

[0580] In the step (12c), the reaction ratio of compound (11c) and the olefin is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the olefin per mole of compound (11c), in consideration of improving the yield and reducing waste.

[0581] The reaction in step (12c) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0582] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

[0583] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0584] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an alcohol or an ether.

[0585] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0586] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0587] The reaction temperature in step (12c) is preferably 40 to 60°C, more preferably 50 to 55°C.

[0588] The reaction pressure in step (12c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0589] The reaction time in step (12c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0590] The elimination reaction of the leaving group in step (13c) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include 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 borofluoride (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0591] The elimination reaction of the leaving group in step (13c) can be carried out in a polar solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0592] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0593] The reaction temperature in step (13c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0594] The reaction pressure in step (13c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0595] The reaction time in step (13c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0596] The oxidation in step (14c) can be carried out in a solvent in the presence of sodium chlorite.

[0597] As the solvent, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butyl alcohol, etc., and water can be used. As the buffer solution, disodium hydrogen phosphate solution can be used.

[0598] Compound (14c) may be contacted with an alkali to convert —COOH to a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and it is preferable to use an aqueous solution of ammonia.

[0599] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0600] The surfactant (c) may also be a compound represented by the formula: [ka] (In the formula, R 3c As mentioned above, R 22c is a monovalent organic group, E c is a leaving group.) and a ketone represented by the formula: [ka] (In the formula, R 1c As mentioned above, R 23c is a monovalent organic group.) to react with a carboxylic acid ester represented by the formula: [ka] (In the formula, R 1c , R 3c and E c As mentioned above, R 24c is a single bond or a divalent linking group, The leaving group of compound (21c) is removed to give a compound of the formula: [ka] (In the formula, R 1c , R 24c and R 3c is as described above.) and Compound (22c) is oxidized to give a compound of the formula: [ka] (In the formula, R 1c , R 24c and R 3c is as described above.) It can be suitably produced by a production method including the steps of:

[0601] R 1cWhen the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0602] E c represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, and a benzyl (Bn) group.

[0603] R 22c As the alkyl group, a linear or branched alkyl group having one or more carbon atoms is preferred, and a methyl group is more preferred. R 23c As the alkyl group, a linear or branched alkyl group having one or more carbon atoms is preferred, and a methyl group is more preferred. R 24c As the alkyl group, a linear or branched alkylene group having one or more carbon atoms is preferred, and a methylene group (—CH2—) is more preferred.

[0604] The reaction in step (21c) can be carried out in a solvent in the presence of a base.

[0605] Examples of the base include sodium amide, sodium hydride, sodium methoxide, and sodium ethoxide.

[0606] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0607] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0608] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0609] The reaction temperature in step (21c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0610] The reaction pressure in the step (21c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0611] The reaction time in step (21c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0612] The elimination reaction of the leaving group in step (22c) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include 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 borofluoride (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0613] The elimination reaction of the leaving group in step (22c) can be carried out in a solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0614] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0615] The reaction temperature in step (22c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0616] The reaction pressure in step (22c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0617] The reaction time in step (22c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0618] The oxidation in step (23c) can be carried out in a solvent in the presence of sodium chlorite.

[0619] The solvent may be alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0620] Compound (23c) may be contacted with an alkali to convert —COOH to a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and it is preferable to use an aqueous solution of ammonia.

[0621] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0622] The surfactant (c) may also be a compound represented by the formula: Y c -R 3c -CH2-OE c (In the formula, R 3c As mentioned above, Y c is a halogen atom, E c is a leaving group.) and an alkyl halide of the formula: [ka] (In the formula, R 1c is as described above.) to form a compound represented by the formula: [ka] (In the formula, R 1c , R 3c and E c is as described above.) Compound (31c) is oxidized to give a compound of formula [ka] (In the formula, R 1c , R 3c and E c is as described above.) to obtain a compound (32c) represented by the formula (32c), The leaving group of compound (32c) is removed to give a compound of the formula: [ka] (In the formula, R 1c and R 3c is as described above.) and Compound (33c) is oxidized to give a compound of formula: [ka] (In the formula, R 1c and R 3c is as described above.) to obtain a compound (34c) represented by the formula (34c), It can be suitably produced by a production method including the steps of:

[0623] R 1cWhen the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0624] E c represents a leaving group. Examples of the leaving group include a tert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, a triisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group, and a benzyl (Bn) group.

[0625] In the step (31c), the reaction ratio of the alkyl halide to the lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles, of the lithium acetylide per mole of the alkyl halide, in consideration of improving yield and reducing waste.

[0626] The reaction in step (31c) can be carried out in a solvent, preferably hexane.

[0627] The reaction temperature in step (31c) is preferably from -100 to -40°C, more preferably from -80 to -50°C.

[0628] The reaction pressure in the step (31c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0629] The reaction time in step (31c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0630] The oxidation in step (32c) is carried out by reacting [(Cn * )Ru III (CF3CO2)3]·H2O (wherein, Cn *This can be carried out in a nitrile solvent using the complex formed by treating 1,4,7-trimethyl-1,4,7-triazabicyclononane (wherein 1,4,7-trimethyl-1,4,7-triazabicyclononane) with (NH4)2Ce(NO3)6 and trifluoroacetic acid, followed by the addition of sodium perchlorate.

[0631] After the oxidation is complete, the reaction mixture may be neutralized with an alkali, and compound (32c) may be extracted using an organic solvent such as ether.

[0632] The reaction temperature in step (32c) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0633] The reaction pressure in step (32c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0634] The reaction time in step (32c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0635] The elimination reaction of the leaving group in step (33c) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include 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 borofluoromethane (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0636] The elimination reaction of the leaving group in step (33c) can be carried out in a solvent, preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an ether.

[0637] 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, tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers (15-crown-5,18-crown-6). Of these, tetrahydrofuran and diethyl ether are preferred.

[0638] The reaction temperature in step (33c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0639] The reaction pressure in the step (33c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0640] The reaction time in step (33c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0641] The oxidation in step (34c) can be carried out in a solvent in the presence of sodium chlorite.

[0642] The solvent may be alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0643] Compound (34c) may be contacted with an alkali to convert —COOH to a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and it is preferable to use an aqueous solution of ammonia.

[0644] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0645] The surfactant (c) may also be a compound represented by the formula: [ka] and a divinyl ketone represented by the formula: [ka] and 2-methylfuran represented by the formula: [ka] Step (51c) of obtaining a compound (51c) represented by Compound (51c) and the formula: [ka] and a furan represented by the formula: [ka] and a step (52c) of obtaining a compound (52c) represented by the formula: [ka] Step (53c) of obtaining a compound (53c) represented by the formula: Compound (53c) is oxidized to give a compound of formula: [ka] Step (54c) of obtaining a compound (54c) represented by It can be suitably produced by a production method including the steps of:

[0646] In the step (51c), the reaction ratio of divinyl ketone and 2-methylfuran is preferably 0.5 to 1 mol, more preferably 0.6 to 0.9 mol, of 2-methylfuran per 1 mol of divinyl ketone, in consideration of improving the yield and reducing waste.

[0647] The reaction in step (51c) is preferably carried out in the presence of an acid, such as acetic acid, hydrochloric acid, or p-toluenesulfonic acid, with acetic acid being preferred.

[0648] The amount of the acid used in step (51c) is preferably 0.1 to 2 mol, more preferably 0.1 to 1 mol, per 1 mol of divinyl ketone, in consideration of improving the yield and reducing waste.

[0649] The reaction in step (51c) can be carried out in a polar solvent, preferably water or acetonitrile.

[0650] The reaction temperature in step (51c) is preferably 20 to 100°C, more preferably 40 to 100°C.

[0651] The reaction pressure in the step (51c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0652] The reaction time in step (51c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0653] In the step (52c), the reaction ratio of compound (51c) and furan is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of furan per mole of compound (51c), in consideration of improving the yield and reducing waste.

[0654] The reaction in step (52c) is preferably carried out in the presence of an acid, such as acetic acid, hydrochloric acid, or p-toluenesulfone, with acetic acid being preferred.

[0655] The amount of the acid used in step (52c) is preferably 0.1 to 2 mol, more preferably 0.1 to 1 mol, per 1 mol of compound (51c), in consideration of improving yield and reducing waste.

[0656] The reaction in step (52c) can be carried out in a polar solvent, preferably water.

[0657] The reaction temperature in step (52c) is preferably 20 to 100°C, more preferably 40 to 100°C.

[0658] The reaction pressure in the step (52c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0659] The reaction time in step (52c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0660] In step (53c), compound (52c) is heated in the presence of an acid to open the furan ring.

[0661] The acid is preferably hydrochloric acid or sulfuric acid.

[0662] The reaction in step (53c) can be carried out in a polar solvent, preferably water.

[0663] The reaction temperature in step (53c) is preferably 50 to 100°C, more preferably 70 to 100°C.

[0664] The reaction pressure in the step (53c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0665] The reaction time in step (53c) is preferably 0.1 to 72 hours, more preferably 1 to 12 hours.

[0666] The oxidation in step (54c) can be carried out in a solvent in the presence of sodium chlorite.

[0667] The solvent may be tert-butyl alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0668] Compound (54c) may be contacted with an alkali to convert —COOH to a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and it is preferable to use an aqueous solution of ammonia.

[0669] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0670] The surfactant (c) may also be a compound represented by the formula: [ka] (In the formula, R 1c As mentioned above, R 21c is a single bond or a divalent linking group.) and an alkene represented by the formula: [ka] (In the formula, Y 61c is an alkyl ester group.) to give an alkyne of the formula: [ka] (In the formula, R 1c , R 21c and Y 61c is as described above.) and Compound (61c) is reacted with an alkali and then with an acid to obtain a compound of the formula: [ka] (In the formula, R 1c and R 21c is as described above.) to obtain a compound (62c) represented by the formula (62c), It can be suitably produced by a production method including the steps of:

[0671] R 1c When the compound contains a furan ring, the furan ring may be opened with an acid to convert it into a dicarbonyl derivative. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfone, and among these, acetic acid is preferred.

[0672] R 21c is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0673] In the step (61c), the reaction ratio of the alkene to the alkyne is preferably 0.5 to 2 moles, more preferably 0.6 to 1.2 moles, of the alkene per mole of the alkyne, in consideration of improving the yield and reducing waste products.

[0674] The reaction in step (61c) is preferably carried out in the presence of a metal catalyst, such as ruthenium.

[0675] The amount of the metal catalyst used in step (61c) is preferably 0.01 to 0.4 mol, more preferably 0.05 to 0.1 mol, per 1 mol of the alkene, in consideration of improving yield and reducing waste.

[0676] The reaction in step (61c) can be carried out in a polar solvent, preferably water, acetonitrile, dimethylacetamide, or dimethylformamide.

[0677] The reaction temperature in step (61c) is preferably 20 to 160°C, more preferably 40 to 140°C.

[0678] The reaction pressure in the step (61c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0679] The reaction time in step (61c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0680] In the step (62c), the reaction ratio of the compound (61c) and the alkali is preferably 0.6 to 2 mol, more preferably 0.8 to 1.1 mol, of the alkali per 1 mol of the compound (61c), in consideration of improving the yield and reducing waste.

[0681] The amount of the acid used in step (62c) is preferably 1.0 to 20.0 mol, more preferably 1.0 to 10.0 mol, per 1 mol of compound (61c), in consideration of improving yield and reducing waste.

[0682] The reaction in step (62c) can be carried out in a polar solvent, preferably water.

[0683] The reaction temperature in step (62c) is preferably 0 to 100°C, more preferably 20 to 100°C.

[0684] The reaction pressure in the step (62c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0685] The reaction time in step (62c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0686] Compound (62c) may be contacted with an alkali to convert —COOH to a salt form. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and it is preferable to use an aqueous solution of ammonia.

[0687] After completion of each step, the purity of the obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0688] The surfactant (d) will now be described.

[0689] In formula (d), R 1d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1dIn the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0690] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0691] R 1d The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0692] R 1d The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0693] R 1d As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0694] In formula (d), R 2d and R 4d are independently H or a substituent. 2d and R 4d may be the same or different.

[0695] R 2d and R 4d The substituent as is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0696] R 2d and R 4d The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0697] R 2d and R 4d The alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0698] R 2d and R 4dare each independently preferably H or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms and not containing a substituent, even more preferably H, a methyl group (-CH3), or an ethyl group (-C2H5), and particularly preferably H.

[0699] In formula (d), R 3d R is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3d When there are a plurality of, they may be the same or different.

[0700] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkylene group preferably does not have any substituents.

[0701] The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, 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 have a substituent, and still more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0702] R 1d , R 2d , R 3d and R 4d Any two of these may be bonded to each other to form a ring.

[0703] In formula (d), n is an integer of 1 or greater. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and even more preferably an integer of 5 to 25.

[0704] In formula (d), p and q are independently an integer of 0 or greater. 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.

[0705] The sum of n, p, and q is preferably an integer of 6 or greater. The sum of n, p, and q is more preferably an integer of 8 or greater. 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 even more preferably an integer of 40 or less.

[0706] In formula (d), A d -SO3X d or -COOX d (X d is H, metal atom, NR 5d 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5d are H or organic groups, and may be the same or different. 5d The organic group in R is preferably an alkyl group. 5d is 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 even more preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred. X d is a metal atom or NR 5d 4(R 5d is as above). X d H, alkali metals (group 1), alkaline earth metals (group 2) or NR 5dX is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. d When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the PTFE or the final product.

[0707] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, or -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group more preferably has 1 to 5 carbon atoms. 6d is more preferably H or a methyl group. d This refers to the side that binds to the

[0708] L is preferably a single bond.

[0709] The surfactant is 1 In the 1 H-NMR spectrum, the integral value of all peak intensities observed in the chemical shift region of 2.0 to 5.0 ppm is preferably 10 or more.

[0710] The surfactant is 1 In the H-NMR spectrum, the integrated value of all peak intensities observed in the chemical shift region of 2.0 to 5.0 ppm is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0711] In the surfactant, the integral value is more preferably 15 or more, and is preferably 95 or less, more preferably 80 or less, and even more preferably 70 or less.

[0712] The above integral value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

[0713] Examples of the surfactant (d) include: CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK, CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa、 CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa、 CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH、CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa、CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2SO3Na、 CH3C(O)CH2CH2SO3Na、 CH3C(O)CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na etc.

[0714] The surfactant (d) is a novel compound and can be produced, for example, by the production method exemplified below.

[0715] The surfactant (d) is represented by the following formula: [ka] (In the formula, R 1d , R 2d and n are as defined above. and a compound (10d) represented by the following formula: [ka] (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- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6dis H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side bonded to -S(=O)2- in the formula. [ka] (In the formula, R 1d ~R 3d , n and X d is as described above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d represents H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents -OSO3X in the formula. d ) The compound (11d) can be suitably produced by a production method including a step (11d) of obtaining a compound (11d) represented by the following formula:

[0716] The reaction in step (11d) can be carried out in the presence of a base. Examples of the base include sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, etc. The base can be used in an amount of 0.5 to 20 moles per mole of compound (10d).

[0717] The reaction in step (11d) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, such as an ether, an aromatic compound, a nitrile, or a halogenated hydrocarbon. Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred. Examples of the aromatic compound include benzene, toluene, and xylene, with benzene being preferred. Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred. Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0718] The reaction temperature in step (11d) is preferably from -78 to 150°C, more preferably from -20 to 100°C.

[0719] The reaction pressure in the step (11d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0720] The reaction time in step (11d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0721] The surfactant (d) may also be a compound represented by the following formula: [ka] (In the formula, R 1d ~R 4d , n, p, and q are as defined above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side which bonds to -CH2-OH in the formula.) Compound (20d) represented by the following formula: [ka] (In the formula, R 1d ~R 4d , n, p, q and X d is as above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents -CH2-COOX in the formula. d ) The compound (21d) can be suitably produced by a production method including a step (21d) of obtaining a compound (21d) represented by the following formula:

[0722] The oxidation in step (21d) can be carried out by reacting compound (20d) with a nitrosating agent.

[0723] As the nitrosating agent, sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite, etc. can be used.

[0724] The nitrosating agent can be used in an amount of 0.5 to 10 moles per mole of compound (20d).

[0725] The oxidation in step (21d) can be carried out in a solvent, such as trifluoroacetic acid or acetonitrile.

[0726] The oxidation temperature in step (21d) is preferably from -78 to 200°C, more preferably from -20 to 100°C.

[0727] The oxidation pressure in the step (21d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0728] The oxidation time in step (21d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 24 hours.

[0729] Compound (10d) and compound (20d) are represented by the following formula: R 11d -CH=CH-Y 1d -OH (In the formula, R 11d is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or 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 defined above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side bonded to -CH2- in the formula. ) is ). Compound (100d) represented by the following formula: [ka] (In the formula, R 11d and Y 1dis as described above.), and Compound (101d) is oxidized to give a compound of the following formula: [ka] (In the formula, R 11d and Y 1d can be produced by a production method including a step (102d) of obtaining a compound (102d) represented by the formula (102d) as described above.

[0730] R 11d The alkyl group as above preferably does not contain a carbonyl group. R 11d The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0731] R 11d is preferably H, a linear or branched alkyl group of 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group of 3 to 9 carbon atoms which may have a substituent; more preferably H, a linear or branched alkyl group of 1 to 9 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group of 3 to 9 carbon atoms which does not contain a carbonyl group; even more preferably H, or a linear or branched alkyl group of 1 to 9 carbon atoms which does not have a substituent; even more preferably H, a methyl group (-CH3), or an ethyl group (-C2H5); particularly preferably H or a methyl group (-CH3), and most preferably H.

[0732] The hydroxylation in step (101d) can be carried out, for example, by (1d) a method of reacting compound (100d) with phthalocyanine iron(II) (Fe(Pc)) and sodium borohydride in an oxygen atmosphere, or (2d) a method of reacting compound (100d) with isopinocampheylborane (IpcBH) and then oxidizing the resulting intermediate (dialkylborane).

[0733] In the method (1d), the amount of phthalocyanine iron(II) may be a catalytic amount, and it can be used in an amount of 0.001 to 1.2 moles per mole of compound (100d).

[0734] In the method (1d), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (100d).

[0735] The reaction of the method (1d) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, an aromatic hydrocarbon, a nitrile, or a nitrogen-containing polar organic compound.

[0736] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0737] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0738] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0739] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0740] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0741] The reaction temperature in the method (1d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0742] The reaction pressure in the method (1d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0743] The reaction time in the method (1d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0744] In the method (2d), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per mole of compound (100d).

[0745] The reaction of compound (100d) with isopinocampheylborane can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0746] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0747] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0748] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0749] The temperature for the reaction of compound (100d) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0750] The pressure for the reaction of compound (100d) with isopinocampheylborane is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0751] The reaction time of compound (100d) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0752] The oxidation in the method (2d) can be carried out by reacting the intermediate with an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide. The oxidizing agent can be used in an amount of 0.7 to 10 moles per mole of the intermediate.

[0753] The oxidation in the method (2d) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0754] The oxidation temperature in the method (2d) is preferably 0 to 100°C, more preferably 0 to 80°C.

[0755] The oxidation pressure in the method (2d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0756] The oxidation time in the method (2d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0757] In step (102d), examples of methods for oxidizing compound (101d) include (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation), (d) 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 (aqueous solution of approximately 5-6% NaOCl) is reacted in the presence of a nickel compound such as NiCl2, and (e) a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0758] The oxidation in step (102d) can be carried out in a solvent, preferably water or an organic solvent, such as water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

[0759] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0760] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0761] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0762] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0763] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0764] The oxidation temperature in the step (102d) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0765] The oxidation pressure in the step (102d) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0766] The oxidation time in step (102d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0767] Compound (10d) and compound (20d) can also be represented by the following formula: [ka] (In the formula, R 1d and Y 1d As mentioned above, R 101d is an organic group.) is decomposed by ozonolysis to obtain a compound (200d) represented by the following formula: [ka] (In the formula, R 1d and Y 1d can be produced by a production method including a step (201d) of obtaining a compound (201d) represented by the formula (201d) as described above.

[0768] R 101d is preferably an alkyl group having 1 to 20 carbon atoms. 101d may be the same or different.

[0769] The ozonolysis in step (201d) can be carried out by reacting compound (200d) with ozone, followed by post-treatment with a reducing agent.

[0770] Ozone can be generated by silent electrical discharge in oxygen gas.

[0771] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0772] The ozonolysis in step (201d) can be carried out in a solvent, preferably water or an organic solvent, such as water, alcohol, carboxylic acids, ethers, halogenated hydrocarbons, and aromatic hydrocarbons.

[0773] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0774] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0775] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0776] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0777] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0778] The temperature for ozonolysis in the step (201d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0779] The pressure for ozonolysis in the step (201d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0780] The time for ozonolysis in the step (201d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0781] Compound (10d) and compound (20d) can also be represented by the following formula: R 21d -CH=CH-Y 1d -OH (In the formula, Y 1d As mentioned above, R 21d is H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring, to thereby obtain a compound (300d) represented by the following formula: [ka] (In the formula, R 21d and Y 1d as described above.), Compound (301d) and R 22d 2CuLi(R 22d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring.) to react with a dialkyl copper lithium represented by the following formula: [ka] (In the formula, R 21d , R 22d and Y 1d is as described above.), and Compound (302d) is oxidized to give a compound of the following formula: [ka] (In the formula, R 21d , R 22d and Y 1dcan be produced by a production method including a step (303d) of obtaining a compound (303d) represented by the formula (303d) as described above.

[0782] R 21d The alkyl group as above preferably does not contain a carbonyl group. R 21d The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0783] R 21d is preferably H, a linear or branched alkyl group of 1 to 8 carbon atoms which may have a substituent, or a cyclic alkyl group of 3 to 8 carbon atoms which may have a substituent; more preferably H, a linear or branched alkyl group of 1 to 8 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group of 3 to 8 carbon atoms which does not contain a carbonyl group; still more preferably H, or a linear or branched alkyl group of 1 to 8 carbon atoms which does not have a substituent; particularly preferably H or a methyl group (—CH3), and most preferably H.

[0784] R 22d The alkyl group as above preferably does not contain a carbonyl group. R 22d The alkyl group as above may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0785] R 22dAs the alkyl group, a linear or branched alkyl group having 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms which may have a substituent, is preferred, a linear or branched alkyl group having 1 to 9 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 9 carbon atoms which does not have a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0786] 2 R's 22d may be the same or different.

[0787] R 21d and R 22d Preferably, the total number of carbon atoms is 1 to 7, more preferably 1 or 2, and most preferably 1.

[0788] The epoxidation in step (301d) can be carried out by reacting compound (300d) with an epoxidizing agent.

[0789] Examples of the epoxidizing agent include metachloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, peracids such as tert-butyl hydroperoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, etc., and among these, peracids are preferred, with metachloroperbenzoic acid being more preferred. The epoxidizing agent can be used in an amount of 0.5 to 10.0 moles per mole of compound (300d).

[0790] The epoxidation in step (301d) can be carried out in a solvent, preferably an organic solvent such as ketone, ether, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, pyridine, nitrogen-containing polar organic compound, dimethyl sulfoxide, etc., with dichloromethane being particularly preferred.

[0791] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0792] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0793] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0794] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0795] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0796] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0797] The epoxidation temperature in the step (301d) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0798] The pressure for epoxidation in the step (301d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0799] The epoxidation time in the step (301d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0800] In the step (302d), the dialkyl copper lithium can be used in an amount of 0.5 to 10.0 moles per mole of the compound (301d).

[0801] The reaction in step (302d) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0802] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0803] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0804] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0805] The reaction temperature in step (302d) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0806] The reaction pressure in step (302d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0807] The reaction time in step (302d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0808] In step (303d), examples of methods for oxidizing compound (302d) include (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation), (d) 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 (aqueous solution of approximately 5-6% NaOCl) is reacted in the presence of a nickel compound such as NiCl2, and (e) a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0809] The oxidation in step (303d) can be carried out in a solvent, preferably water or an organic solvent, such as water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

[0810] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0811] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0812] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0813] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0814] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0815] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0816] The oxidation temperature in step (303d) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0817] The oxidation pressure in the step (303d) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0818] The oxidation time in step (303d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0819] Compound (10d) and compound (20d) can also be represented by the following formula: R 11d -CH=CH-Y 1d -OH (In the formula, R 11d and Y 1d is as described above.) is oxidized to obtain a compound (100d) represented by the following formula: [ka] (In the formula, R 11d and Y 1d can be produced by a production method including a step (401d) of obtaining a compound (401d) represented by the formula (401d) as described above.

[0820] The oxidation in step (401d) can be carried out by treating compound (100d) with an oxidizing agent in the presence of water and a palladium compound.

[0821] Examples of the oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide, copper trifluoromethanethiol, etc., iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanethiol, iron hexacyano, etc., benzoquinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, etc., HO, MnO, KMnO, RuO, m-chloroperbenzoic acid, oxygen, etc. Among these, copper salts, iron salts, and benzoquinones are preferred, and copper chloride, iron chloride, and 1,4-benzoquinone are more preferred. The oxidizing agent can be used in an amount of 0.001 to 10 moles per mole of compound (100d).

[0822] The water can be used in an amount of 0.5 to 1000 moles per mole of compound (100d).

[0823] The palladium compound may be palladium dichloride. The amount of the palladium compound may be a catalytic amount, and it can be used in an amount of 0.0001 to 1.0 mol per 1 mol of compound (100d).

[0824] The oxidation in step (401d) can be carried out in a solvent, such as water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, or sulfolane.

[0825] Examples of the ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and among these, ethyl acetate is preferred.

[0826] Examples of the aliphatic hydrocarbon include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc., and among these, cyclohexane and heptane are preferred.

[0827] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0828] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0829] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0830] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0831] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0832] Examples of the nitrogen-containing polar organic compound include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, and among these, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred.

[0833] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0834] The oxidation temperature in the step (401d) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0835] The oxidation pressure in the step (401d) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0836] The oxidation time in the step (401d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0837] The surfactant (d) may also be a compound represented by the following formula: R 11d -CH=CH-(CR 2d 2) n -(OR 3d ) p -(CR 4d 2) q -L-COOX d (In the formula, R 2d ~R 4d , R 11d , n, p, q and X d is as above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkylene group more preferably has 1 to 5 carbon atoms. 6d is more preferably H or a methyl group. * represents -COOX in the formula. d (referring to the side bonded to the compound (30d)) is oxidized to obtain a compound (30e) represented by the following formula: [ka] (R 2d ~R 4d , L, R 11d , n, p, q and X d can be produced by a production method including a step (31d) of obtaining a compound (31d) represented by the formula (31d) as described above.

[0838] The oxidation in step (31d) can be carried out by reacting compound (30d) with an oxidizing agent in the presence of water and a palladium compound, and the same conditions as those for the oxidation in step (401d) can be used.

[0839] In any of the above-mentioned production methods, after completion of each step, the purity of the obtained compound may be increased by distilling off the solvent, or by carrying out distillation, purification, etc. Furthermore, if the obtained compound does not contain X such as -SO3H or -COOH, d For compounds where is H, these groups can be converted to the salt form by contacting with an alkali such as sodium carbonate or ammonia.

[0840] In the production method of the present disclosure, two or more of the above hydrocarbon surfactants may be used simultaneously.

[0841] The polymerization step is a step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of a specific hydrocarbon surfactant, and it is also preferable that the step includes a step of continuously adding the specific hydrocarbon surfactant. The specific hydrocarbon surfactant is, for example, the above-mentioned surfactant (1), the above-mentioned hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) to radical treatment or oxidation treatment. The specific hydrocarbon surfactant is also preferably the above-mentioned hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) or a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) to radical treatment or oxidation treatment. By adopting the above method, it is possible to obtain an aqueous dispersion having a smaller average primary particle size and excellent stability. Also, it is possible to obtain an aqueous dispersion having a smaller amount of uncoagulated polymer. Furthermore, it is possible to reduce the aspect ratio of the primary particles.

[0842] The present disclosure also provides polytetrafluoroethylene obtained by a production method comprising the steps of: polymerizing tetrafluoroethylene and a modifying monomer in an aqueous medium in the presence of a specific hydrocarbon surfactant; and continuously adding the specific hydrocarbon surfactant during the polymerization step.

[0843] In the step of continuously adding the specific hydrocarbon surfactant, it is preferable to start adding the specific hydrocarbon surfactant to the aqueous medium when the concentration of PTFE formed in the aqueous medium is less than 0.60% by mass. The specific hydrocarbon surfactant is more preferably started when the concentration is 0.50% by mass or less, even more preferably when it is 0.36% by mass or less, even more preferably when it is 0.30% by mass or less, even more preferably when it is 0.20% by mass or less, particularly preferably when it is 0.10% by mass or less, and most preferably when the polymerization starts. The above concentration is the concentration relative to the total of the aqueous medium and PTFE.

[0844] In the step of continuously adding the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant added is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium, more preferably 0.05% by mass at the lower limit, even more preferably 0.1% by mass at the lower limit, more preferably 5% by mass at the upper limit, and even more preferably 1% by mass at the upper limit.

[0845] In the step of polymerizing tetrafluoroethylene and a modified monomer in an aqueous medium in the presence of the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant is preferably large, and is preferably 0.01 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferred lower limit is 0.1% by mass, and a more preferred upper limit is 1% by mass.

[0846] The specific hydrocarbon surfactant is preferably at least one selected from the group consisting of surfactant (1) represented by general formula (1) above, surfactant (a) represented by formula (a), surfactant (b) represented by formula (b), surfactant (c) represented by formula (c), surfactant (d) represented by formula (d), and surfactants obtained by subjecting these surfactants (a) to (d) to radical treatment or oxidation treatment, and more preferably at least one selected from the group consisting of surfactant (a) represented by formula (a), surfactant (b) represented by formula (b), surfactant (c) represented by formula (c), surfactant (d) represented by formula (d), and surfactants obtained by subjecting these surfactants (a) to (d) to radical treatment or oxidation treatment.

[0847] The hydrocarbon surfactant used in the manufacturing method of the present disclosure is preferably a carboxylic acid hydrocarbon surfactant. Carboxylic acid hydrocarbon surfactants tend to have a shorter coagulation completion time than sulfate ester surfactants. However, according to the manufacturing method of the present disclosure, even when a carboxylic acid hydrocarbon surfactant is used, an aqueous dispersion having a long coagulation completion time can be manufactured. That is, the production method of the present disclosure is particularly suitable when the hydrocarbon surfactant is a carboxylic acid type hydrocarbon surfactant. The carboxylic acid type hydrocarbon surfactant is usually an anionic hydrocarbon surfactant having a hydrophilic portion of a carboxylate salt and a hydrophobic portion of a long-chain hydrocarbon portion such as an alkyl. Specifically, it is not limited as long as it has a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.), and for example, from among the above-mentioned hydrocarbon surfactants, a hydrocarbon surfactant having a carboxyl group or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation can be used.

[0848] The carboxylic acid type hydrocarbon surfactant may be an aliphatic carboxylic acid type hydrocarbon surfactant, or may be a non-aliphatic carboxylic acid type hydrocarbon surfactant. In this specification, the term "aliphatic carboxylic acid type hydrocarbon surfactant" refers to a carboxylic acid type hydrocarbon surfactant that does not contain a carbonyl group (excluding carbonyl groups in carboxyl groups and ester groups). The ester group refers to a group represented by -COO- or -OCO-. As the carboxylic acid type hydrocarbon surfactant, for example, from among the hydrocarbon surfactants described above, a hydrocarbon surfactant having a carboxyl group or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation can be used. The carboxylic acid type hydrocarbon surfactant that may be used in the polymerization step and the addition step includes the surfactant (1), the surfactant of the above formula: R 6z (-LM)2 and anionic surfactants represented by the above formula: R 7zAmong the anionic surfactants represented by (-LM)3, at least one selected from the group consisting of those having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.), the above compound (α), the above surfactant (1-0A), and surfactants obtained by radical treatment or oxidation treatment of these surfactants is preferred. The above carboxylic acid type hydrocarbon surfactants may be used alone or as a mixture of two or more types. The compound (α) has the above-mentioned formula: R 100 -COOM(in the formula, R 100 and M are the same as above.) (preferably, the compound represented by formula (A)), as well as the anionic hydrocarbon surfactant represented by the above formula: R z -LM (where R z , L and M are the same as above), and among the surfactants (c) and (d), those having a carboxyl group (-COOH) or a group in which the hydrogen atom of the carboxyl group is substituted with an inorganic cation (e.g., a metal atom, ammonium, etc.).

[0849] The carboxylic acid type hydrocarbon surfactant is preferably the compound (α), and is preferably a compound represented by the formula (A), a compound represented by the formula (c), c Ga-COOX c A compound represented by the formula (d) d Ga-COOX d a compound represented by the above formula (1) where A is -COOM; a compound represented by the above formula (1-0A) where A is -COOM; and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment, and further preferably at least one selected from the group consisting of a compound represented by the above formula (A) and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment. In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, salts thereof, and compounds obtained by radical treatment or oxidation treatment of these compounds is preferred, at least one selected from the group consisting of lauric acid, salts thereof, and compounds obtained by radical treatment or oxidation treatment of these compounds is more preferred, at least one selected from the group consisting of salts of lauric acid and compounds obtained by radical treatment or oxidation treatment of these compounds is even more preferred, and at least one selected from the group consisting of sodium laurate and compounds obtained by radical treatment or oxidation treatment of these salts is even more preferred. As the above salts, there are preferred salts in which the hydrogen of the carboxyl group is bonded to a metal atom of the above formula M, NR 101 4. Examples include, but are not limited to, imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent.

[0850] The carboxylic acid type hydrocarbon surfactant is preferably at least one selected from the group consisting of surfactant (1-0A) represented by general formula (1-0A) above, compound (α) above, surfactant (c) represented by formula (c) above, and surfactant (d) represented by formula (d) above.

[0851] As the hydrocarbon surfactant, a hydrocarbon surfactant obtained by subjecting the carboxylic acid type hydrocarbon surfactant to radical treatment or oxidation treatment can also be used. As the carboxylic acid type hydrocarbon surfactant, the compound (α) is preferred. The radical treatment may be any treatment that generates radicals in a carboxylic acid hydrocarbon surfactant. For example, it is a treatment in which deionized water and a carboxylic acid hydrocarbon surfactant are added to a reactor, the reactor is sealed, the system is purged with nitrogen, the temperature and pressure of the reactor are increased, a polymerization initiator is added, the mixture is stirred for a certain period of time, the pressure of the reactor is reduced to atmospheric pressure, and the mixture is cooled. The oxidation treatment is a treatment in which an oxidizing agent is added to the carboxylic acid hydrocarbon surfactant. Examples of oxidizing agents include oxygen, ozone, hydrogen peroxide, manganese (IV) oxide, potassium permanganate, potassium dichromate, nitric acid, and sulfur dioxide.

[0852] The PTFE production method of the present disclosure may further include a step of adjusting the pH of the aqueous medium containing the hydrocarbon surfactant to a basic value. The basic value is preferably 7.1 or higher, more preferably 7.5 or higher, even more preferably 8.0 or higher, particularly preferably 8.5 or higher, and even more preferably 9.0 or higher. Adjusting the pH to a basic value can enhance the surface activity. The pH adjustment step may be performed before or after the step of radical treatment or oxidation treatment of the carboxylic acid-type hydrocarbon surfactant, but is preferably performed after. The method for adjusting the pH is not particularly limited, but examples include adding a pH adjuster to the aqueous medium. Examples of pH adjusters that can be used include ammonia, an aqueous NaOH solution, an aqueous potassium hydroxide solution, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium phosphate, potassium phosphate, sodium citrate, potassium citrate, ammonium citrate, sodium gluconate, potassium gluconate, and ammonium gluconate. The pH can be measured using an Orion pH meter.

[0853] The polymerization step is also preferably carried out in an aqueous medium having a pH of 4.0 or higher in the presence of a hydrocarbon surfactant and a polymerization initiator. It is preferable to carry out the polymerization in an aqueous medium having a pH of 4.0 or higher. Conventionally, polymerization initiators exhibiting acidity have been used in polymerization steps for producing polytetrafluoroethylene, so the pH of the aqueous medium used in the polymerization was less than 4.0. Through extensive research, the present inventors have unexpectedly found that adjusting the pH of the aqueous medium used in the polymerization to 4.0 or higher improves the stability of the polymerization, enabling the production of polytetrafluoroethylene with a high molecular weight. The pH may be 4.0 or higher, preferably greater than 4.0, more preferably 4.5 or higher, even more preferably 5.0 or higher, even more preferably 5.5 or higher, particularly preferably 6.0 or higher, particularly preferably 6.5 or higher, particularly preferably 7.0 or higher, particularly preferably 7.5 or higher, and particularly preferably 8.0 or higher. The upper limit of the pH is not particularly limited, but may be, for example, 13.0 or lower. From the viewpoint of corrosion of the polymerization vessel, it is preferably 12.0 or lower, more preferably 11.5 or lower, and even more preferably 11.0 or lower. The pH can be measured using a pH meter. In the polymerization step, the hydrocarbon surfactant is preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid type hydrocarbon surfactant.

[0854] The method for adjusting the pH of the aqueous medium to 4.0 or higher is not particularly limited, but for example, the pH can be adjusted to 4.0 or higher by using an alkaline aqueous solution, an alkaline aqueous dispersion, or a pH adjuster, but is not particularly limited. Even when a polymerization initiator that is acidic when dissolved in an aqueous medium is used, the pH can be adjusted to 4.0 or higher by further adding an alkaline compound such as sodium hydroxide. The alkaline compound is, for example, a compound that dissolves in water and ionizes to form OH groups. -Any compound capable of generating the above-mentioned polymerization reaction may be used, and examples thereof include, but are not limited to, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc. The polymerization step may include a step of adding an alkali compound to the aqueous medium.

[0855] The pH of the aqueous medium may be 4.0 or higher throughout the entire polymerization process. Alternatively, the pH may be 4.0 or higher in the middle of the polymerization process, or at the end of the polymerization process. Alternatively, the pH may be 4.0 or higher both in the middle and at the end of the polymerization process. For example, in the polymerization step, the pH of the aqueous medium is preferably 4.0 or higher when the polymer solids concentration is 3% by mass or higher. In other words, the polymerization step is a step of polymerizing a fluoromonomer in an aqueous medium in the presence of a hydrocarbon surfactant to obtain a fluoropolymer, and in the polymerization step, the aqueous medium preferably has a pH of 4.0 or higher when the polymer solids concentration is 3% by mass or higher. The aqueous medium more preferably has a pH of 4.0 or higher when the polymer solids concentration is 5% by mass or higher, even more preferably has a pH of 4.0 or higher when the polymer solids concentration is 8% by mass or higher, even more preferably has a pH of 4.0 or higher when the polymer solids concentration is 10% by mass or higher, especially preferably has a pH of 4.0 or higher when the polymer solids concentration is 15% by mass or higher, particularly preferably has a pH of 4.0 or higher when the polymer solids concentration is 18% by mass or higher, more preferably has a pH of 4.0 or higher when the polymer solids concentration is 20...

Claims

1. The method includes a polymerization step of obtaining polytetrafluoroethylene by 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 is 60 ppm or more relative to the aqueous medium, The polymerization step includes continuously adding a hydrocarbon surfactant; 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 a modified monomer. A method for producing polytetrafluoroethylene, comprising the steps of:

2. The method according to claim 1, further comprising the step of adding a modifying monomer to the aqueous medium before the initiation of polymerization or when the concentration of polytetrafluoroethylene formed in the aqueous medium is 5.0% by mass or less.

3. 3. The method according to claim 2, wherein the amount of the modifying 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 based on the polytetrafluoroethylene obtained.

4. In the polymerization process, the number of polytetrafluoroethylene particles is 0.6 × 10 １３ The method according to any one of claims 1 to 3, wherein the concentration of the serotonin-containing compound is 1 / mL or more.

5. The method according to any one of claims 1 to 4, wherein in the step of continuously adding the hydrocarbon surfactant, when the concentration of polytetrafluoroethylene formed in the aqueous medium is less than 0.6 mass%, the addition of the hydrocarbon surfactant to the aqueous medium is started.

6. The method according to any one of claims 1 to 5, wherein the polymerization temperature in the polymerization step is 10 to 150°C.

7. The method according to any one of claims 1 to 6, wherein the modified monomer comprises at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene.

8. The modified monomer includes a modified monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group, The hydrophilic group is -COOM (wherein M is H, a metal atom, or NR ７ｙ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ｙ are H or an organic group and may be the same or different. Any two of them may be bonded to each other to form a ring.

9. The modifying monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group is represented by the following formula (4): CX ｉ X ｋ =CX ｊ R ａ -(CZ １ Z ２ ) ｋ -Y ３ (4) (In the formula, X ｉ , X ｊ and X ｋ are each independently F, Cl, H or CF ３ and Y ３ is a hydrophilic group; R ａ is a linking group; Z １ and Z ２ are each independently H, F or CF ３ and k is 0 or 1, The hydrophilic group is -COOM (wherein M is H, a metal atom, or NR ７ｙ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ｙ are H or an organic group and may be the same or different. Any two of them may be bonded to each other to form a ring; The method according to claim 8, wherein the linking group is a hydrocarbon group in which all of the hydrogen atoms bonded to carbon atoms have been substituted with fluorine atoms and which may contain an oxygen atom.

10. The method according to any one of claims 1 to 9, wherein the hydrocarbon surfactant is a carboxylic acid type hydrocarbon surfactant.

11. The method according to any one of claims 1 to 10, wherein the polymerization step is carried out in an aqueous medium containing a fluorine-containing surfactant (excluding a modified monomer having a functional group reactive by radical polymerization and a hydrophilic group) at 10 ppm or less.

12. The method according to any one of claims 1 to 11, wherein the polytetrafluoroethylene has a core-shell structure.

13. The method according to any one of claims 1 to 12, wherein the polytetrafluoroethylene has an average primary particle size of 500 nm or less.

14. The method according to any one of claims 1 to 9, wherein the polytetrafluoroethylene has a primary particle aspect ratio of 1.45 or less.

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