Polytetrafluoroethylene and its extensions

Abstract

Provided is polytetrafluoroethylene with excellent stretchability. The polytetrafluoroethylene is characterized by a standard specific gravity of 2.175 or less and a thermal instability index (TII) of 20 or more.

Description

[Technical Field]

[0001] The present disclosure relates to polytetrafluoroethylene and expanded bodies. [Background technology]

[0002] When polytetrafluoroethylene is molded and highly stretched in an unsintered state, a porous polytetrafluoroethylene film is obtained. This porous film allows gases such as water vapor to pass through, but does not allow water droplets to pass through due to the strong water repellency of polytetrafluoroethylene. This unique property is used in applications such as clothing and separation membranes.

[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.

[0006] Patent Document 4 describes a method for reducing thermally induced discoloration of a fluoropolymer resin, the fluoropolymer resin being produced by the steps of polymerizing a fluoromonomer in an aqueous dispersion medium to form an aqueous fluoropolymer dispersion, isolating the fluoropolymer from the aqueous medium by separating the fluoropolymer resin in wet form from the aqueous medium, and drying to produce a fluoropolymer resin in dry form, the method comprising the step of exposing the fluoropolymer resin in wet or dry form to an oxidizing agent. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2013-542308 [Patent Document 2] Special Publication No. 2013-542309 [Patent Document 3] Special Publication No. 2013-542310 [Patent Document 4] International Publication No. 2013 / 169581 Summary of the Invention [Problem to be solved by the invention]

[0008] The present disclosure provides polytetrafluoroethylene having excellent stretchability and an expanded body made of the polytetrafluoroethylene, preferably having excellent breaking strength and stress relaxation time. [Means for solving the problem]

[0009] The present disclosure relates to polytetrafluoroethylene characterized by a standard specific gravity of 2.175 or less and a thermal instability index (TII) of 20 or more. The present disclosure also relates to polytetrafluoroethylene characterized by a standard specific gravity of 2.175 or less and a 0.1% mass loss temperature of 400°C or less. The present disclosure also relates to polytetrafluoroethylene characterized by a standard specific gravity of 2.175 or less and a 1.0% mass loss temperature of 492°C or less. The present disclosure also relates to polytetrafluoroethylene characterized by a breaking strength of 10.0 N or more and a thermal instability index (TII) of 20 or more. The present disclosure also relates to polytetrafluoroethylene characterized by a breaking strength of 10.0 N or more and a 0.1% mass loss temperature of 400° C. or less. The present disclosure also relates to polytetrafluoroethylene characterized by a breaking strength of 10.0 N or more and a 1.0% mass loss temperature of 492°C or less. The polytetrafluoroethylene of the present disclosure preferably has a stress relaxation time of 50 seconds or more. The polytetrafluoroethylene of the present disclosure preferably has an extrusion pressure of 30.0 MPa or less. The polytetrafluoroethylene of the present disclosure is preferably such that the lightness L* of a sheet cut out from a sintered body obtained by molding the polytetrafluoroethylene and heat-treating it at 100°C for 2 hours, at 200°C for 4 hours, and at 370°C for 5 hours is 90.0 or less. The polytetrafluoroethylene of the present disclosure preferably has a thermal shrinkage rate of 7.0% or more when sintered by molding the polytetrafluoroethylene and heat-treating it at 100°C for 2 hours, at 200°C for 4 hours, and at 370°C for 5 hours. The polytetrafluoroethylene of the present disclosure is preferably such that a contact angle of a surface corresponding to the inside of a sintered body of a sheet cut out from the sintered body obtained by molding the polytetrafluoroethylene and heat-treating it at 100°C for 2 hours, at 200°C for 4 hours, and at 370°C for 5 hours is 107° or more. The polytetrafluoroethylene of the present disclosure is preferably in the form of a powder. The present disclosure also relates to an expanded body made of the above-mentioned polytetrafluoroethylene. [Effects of the Invention]

[0010] The polytetrafluoroethylene of the present disclosure has the above-described structure, and therefore has excellent stretchability. The stretched body of the present disclosure has the above-described structure, and therefore has excellent breaking strength and stress relaxation time. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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-, RaOSO2- and, RaNRbSO2- (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; Rb is independently H or an alkyl group which may have one or more substituents. Includes. The organic group is preferably an alkyl group which may have one or more substituents.

[0012] In addition, in this specification, the term "substituent" means a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an These include an amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thio group, an aromatic thio group, a hydroxy group, a cyano group, a sulfo group, a carboxy group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaromatic oxyphosphinyl group.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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 methoxycarbonyl, ethoxycarbonyl, and (t)-butoxycarbonyl groups.

[0019] 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.

[0020] 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 methanesulfonyl.

[0021] 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.

[0022] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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, or an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0028] 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.

[0029] 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.

[0030] Further herein, ranges expressed by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0031] Further, as used herein, references to "at least 1" include all numbers greater than or equal to 1 (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0032] Next, the polytetrafluoroethylene of the present disclosure will be specifically described.

[0033] The polytetrafluoroethylene (hereinafter sometimes referred to as "PTFE") of the present disclosure has a standard specific gravity of 2.175 or less and a thermal instability index (TII) of 20 or more. (Hereinafter sometimes referred to as the first PTFE of the present disclosure.) The first PTFE of the present disclosure preferably has a breaking strength of 10.0 N or more. The first PTFE of the present disclosure may have a 0.1% mass loss temperature of 400°C or less. The first PTFE of the present disclosure may have a 1.0% mass loss temperature of 492°C or less.

[0034] The PTFE of the present disclosure also has a standard specific gravity of 2.175 or less and a 0.1% mass loss temperature of 400°C or less (hereinafter, sometimes referred to as the second PTFE of the present disclosure). The second PTFE of the present disclosure preferably has a breaking strength of 10.0 N or more. The second PTFE of the present disclosure preferably has a thermal instability index (TII) of 20 or more. The second PTFE of the present disclosure may have a 1.0% mass loss temperature of 492°C or less.

[0035] The PTFE of the present disclosure also has a standard specific gravity of 2.175 or less and a 1.0% mass loss temperature of 492°C or less (hereinafter, sometimes referred to as the third PTFE of the present disclosure). The third PTFE of the present disclosure preferably has a breaking strength of 10.0 N or more. The third PTFE of the present disclosure preferably has a thermal instability index (TII) of 20 or more. The third PTFE of the present disclosure may have a 0.1% mass loss temperature of 400°C or less.

[0036] The first to third PTFEs of the present disclosure have a standard specific gravity (SSG) of 2.175 or less, making them suitable for stretch molding, and also enabling the production of stretched bodies with excellent breaking strength and stress relaxation time.

[0037] The PTFE of the present disclosure also has a breaking strength of 10.0 N or more and a thermal instability index (TII) of 20 or more (hereinafter, sometimes referred to as the fourth PTFE of the present disclosure). The fourth PTFE of the present disclosure preferably has a standard specific gravity of 2.175 or less. The fourth PTFE of the present disclosure may have a 0.1% mass loss temperature of 400°C or less. The fourth PTFE of the present disclosure may have a 1.0% mass loss temperature of 492°C or less.

[0038] The PTFE of the present disclosure also has a breaking strength of 10.0 N or more and a 0.1% mass loss temperature of 400°C or less (hereinafter, sometimes referred to as the fifth PTFE of the present disclosure). The fifth PTFE of the present disclosure preferably has a standard specific gravity of 2.175 or less. The fifth PTFE of the present disclosure preferably has a thermal instability index (TII) of 20 or more. The fifth PTFE of the present disclosure may have a 1.0% mass loss temperature of 492°C or less.

[0039] The PTFE of the present disclosure also has a breaking strength of 10.0 N or more and a 1.0% mass loss temperature of 492°C or less (hereinafter, sometimes referred to as the sixth PTFE of the present disclosure). The sixth PTFE of the present disclosure preferably has a standard specific gravity of 2.175 or less. The sixth PTFE of the present disclosure preferably has a thermal instability index (TII) of 20 or more. The sixth PTFE of the present disclosure may have a 0.1% mass loss temperature of 400°C or less.

[0040] The fourth to sixth PTFEs of the present disclosure are suitable for stretch molding because they have a breaking strength of at least 10.0 N. Furthermore, stretched bodies excellent in breaking strength and stress relaxation time can be obtained.

[0041] The PTFE of the present disclosure also has a breaking strength of 10.0 N or more and is substantially free of fluorine-containing surfactants (hereinafter, sometimes referred to as the seventh PTFE of the present disclosure). The seventh PTFE of the present disclosure preferably has a standard specific gravity of 2.175 or less. The seventh PTFE of the present disclosure preferably has a thermal instability index (TII) of 20 or more. The seventh PTFE of the present disclosure may have a 0.1% mass loss temperature of 400°C or less. The seventh PTFE of the present disclosure may have a 1.0% mass loss temperature of 492°C or less.

[0042] The PTFE of the present disclosure also has a standard specific gravity of 2.175 or less and is substantially free of fluorine-containing surfactants (hereinafter, sometimes referred to as the eighth PTFE of the present disclosure). The eighth PTFE of the present disclosure preferably has a breaking strength of 10.0 N or more. The eighth PTFE of the present disclosure preferably has a thermal instability index (TII) of 20 or more. The eighth PTFE of the present disclosure may have a 0.1% mass loss temperature of 400°C or less. The eighth PTFE of the present disclosure may have a 1.0% mass loss temperature of 492°C or less.

[0043] The seventh and eighth PTFEs of the present disclosure are suitable for stretch molding because they are substantially free of a fluorine-containing surfactant, and can give stretched bodies excellent in breaking strength and stress relaxation time.

[0044] In this specification, unless otherwise specified, "PTFE of the present disclosure" means PTFEs 1 to 8 of the present disclosure.

[0045] The PTFE of the present disclosure has a standard specific gravity (SSG) of 2.175, preferably 2.170 or less, more preferably 2.165 or less, even more preferably 2.160 or less, and may be 2.155 or less. The SSG is measured by the water displacement method in accordance with ASTM D-792 using a sample molded in accordance with ASTM D 4895-89.

[0046] PTFE having a thermal instability index (TII) of 20 or more 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. 40 or more is particularly preferred. The TII is measured in accordance with ASTM D 4895-89.

[0047] PTFE having a 0.1% mass loss temperature of 400° C. or less 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 simultaneous differential thermal analyzer). The 0.1% mass loss temperature was determined as the temperature at which a 0.1% mass 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.

[0048] PTFE having a 1.0% mass loss temperature of 492° C. or less 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 weighed out and placed in a special aluminum pan for measurement using a TG / DTA (thermogravimetric and 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.

[0049] The PTFE of the present disclosure preferably has an average primary particle diameter of 150 nm or more, more preferably 180 nm or more. The larger the average primary particle diameter of PTFE, the more suppressed the increase in paste extrusion pressure when paste extrusion molding is performed using the powder, and the better the film-forming properties. The upper limit is not particularly limited, but may be 500 nm. From the viewpoint of productivity in the polymerization process, the upper limit is preferably 350 nm. The average primary particle diameter is determined by preparing a calibration curve by diluting an aqueous PTFE dispersion with water to a solid content of 0.15% by mass, measuring the transmittance of 550 nm incident light per unit length of the resulting diluted latex, and measuring the number-average particle diameter determined by measuring the unidirectional diameter using a transmission electron microscope photograph, and then using this calibration curve to determine the actual transmittance of 550 nm incident light for each sample.

[0050] The PTFE of the present disclosure has an extrusion pressure of preferably 30.0 MPa or less, more preferably 29.0 MPa or less, even more preferably 28.0 MPa or less, even more preferably 25.0 MPa or less, preferably 5.0 MPa or more, and more preferably 10.0 MPa or more. The extrusion pressure is a value determined by the following method in accordance with the method described in JP 2002-201217 A. 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 a reduction ratio of 100:1 at room temperature 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.

[0051] The PTFE of the present disclosure is preferably expandable. In this specification, "expandable" is determined according to the following criteria. The bead obtained by the paste extrusion described above is heated at 230°C for 30 minutes to remove the lubricant from the bead. The bead (extrudate) is then cut to an appropriate length, clamped at each end with a clamp spacing of 1.5 inches (38 mm), and heated to 300°C in an air-circulating oven. The clamps are then separated at a desired speed (stretch rate) until a separation distance corresponding to the desired stretch (total stretch) is reached, and a stretch test (orientation test) is performed. This stretching method essentially follows the method disclosed in U.S. Pat. No. 4,576,869, except for the extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" refers to the increase in length due to stretching and is usually expressed relative to the original length. In the above production method, the stretch rate is 1000% / sec, and the total stretch is 2400%. This stretch test results in a stretched bead with a uniform appearance without breakage.

[0052] The PTFE of the present disclosure preferably has a breaking strength of 13.0 N or more, more preferably 16.0 N or more, even more preferably 19.0 N or more, even more preferably 22.0 N or more, even more preferably 23.0 N or more, even more preferably 25.0 N or more, even more preferably 28.0 N or more, even more preferably 29.0 N or more, even more preferably 30.0 N or more, even more preferably 32.0 N or more, even more preferably 35.0 N or more, even more preferably 37.0 N or more, and even more preferably 40.0 N or more. The higher the breaking strength, the better, but it may be 100.0 N or less, 80.0 N or less, or 50.0 N or less. The breaking strength is a value determined by the following method. The stretched bead (produced by stretching the bead) obtained in the above stretching test is clamped and fixed between movable jaws with a gauge length of 5.0 cm, and a tensile test is performed at 25°C and a speed of 300 mm / min. The strength at which it breaks is taken as the breaking strength.

[0053] The PTFE of the present disclosure has a stress relaxation time of preferably 50 seconds or more, more preferably 80 seconds or more, and even more preferably 100 seconds or more, and may be 120 seconds or more, 150 seconds or more, 190 seconds or more, 200 seconds or more, 220 seconds or more, 240 seconds or more, or 300 seconds or more. The stress relaxation time is a value measured by the following method. Both ends of the stretched bead obtained in the stretch test above are connected to a fixture to create a taut bead sample with a total length of 8 inches (20 cm). The oven is maintained at 390°C and the fixture is inserted into the oven through a (covered) slit in the side of the oven. The time required from the time of insertion into the oven until the bead sample breaks is the stress relaxation time.

[0054] The PTFE of the present disclosure may have a lightness L* of 90.0 or less, 80 or less, 70 or less, 60 or less, or 50 or less when cut out from a sintered body obtained by molding the PTFE and heat-treating it at 100°C for 2 hours, at 200°C for 4 hours, and at 370°C for 5 hours. The lightness L* is a value measured by the following method. Fill a mold with an inner diameter of 50 mm with 210 g of powder, and apply pressure of approximately 200 kg / cm for approximately 30 seconds. 2 Pressure was applied until the temperature reached a certain value, and the pressure was maintained for an additional 5 minutes to produce a preform. The preform was removed from the mold and heat-treated in a hot air circulation electric furnace at 100°C for 2 hours, 200°C for 4 hours, and 370°C for 5 hours. The temperature was then lowered to room temperature at a rate of 50°C / hour to produce a cylindrical fired body. This fired body was then machined along its side to produce a strip-shaped sheet with a thickness of 0.5 mm. A test piece measuring 100 mm x 50 mm was cut from this strip-shaped sheet, and the lightness (L*) of the strip-shaped sheet was measured using a colorimeter (CR-400, manufactured by Konica Minolta Optics, Inc.).

[0055] The PTFE of the present disclosure may have a heat shrinkage rate of 7.0% or more, or may be 6.5% or more, of a sintered body obtained by molding the PTFE and heat-treating it at 100°C for 2 hours, at 200°C for 4 hours, and at 370°C for 5 hours. The heat shrinkage rate is a value measured by the following method. Fill a mold with an inner diameter of 50 mm with 210 g of powder, and apply pressure of approximately 200 kg / cm for approximately 30 seconds. 2 Pressure was applied until the temperature reached a constant value, and the pressure was maintained for an additional 5 minutes to produce a preform. The preform was removed from the mold, and its diameter (A) was measured. The preform was then heat-treated in a hot-air circulation electric furnace at 100°C for 2 hours, 200°C for 4 hours, and 370°C for 5 hours, and then cooled to room temperature at a rate of 50°C / hour to obtain a cylindrical sintered body. The diameter (B) of the resulting sintered body was measured, and the thermal shrinkage was calculated using the following formula. Heat shrinkage rate = ((A) - (B)) / (A)*100

[0056] The PTFE of the present disclosure is formed by molding PTFE and heat-treating it at 100°C for 2 hours, at 200°C for 4 hours, and at 370°C for 5 hours, and the contact angle of the surface of the sheet cut out from the sintered body, which corresponds to the inside of the sintered body, is preferably 107° or more, more preferably 108° or more, even more preferably 109° or more, and particularly preferably 110° or more. The above contact angle is a value measured by the following method. Fill a mold with an inner diameter of 50 mm with 210 g of powder, and apply pressure of approximately 200 kg / cm for approximately 30 seconds. 2Pressure was applied until the temperature reached a certain value, and the pressure was maintained for an additional 5 minutes to produce a preform. The preform was removed from the mold and heat-treated in a hot-air circulation electric furnace at 100°C for 2 hours, 200°C for 4 hours, and 370°C for 5 hours. The temperature was then lowered to room temperature at a rate of 50°C / hour to produce a cylindrical sintered body. This sintered body was then machined along its side to produce a 0.5 mm thick strip. A 50 mm x 50 mm test piece was cut from this strip, and the contact angle of the surface corresponding to the inside of the strip was measured using a portable contact angle meter (PCA-1, manufactured by Kyowa Interface Science Co., Ltd.). The contact angle was calculated by placing a water droplet on the test piece, capturing an image of the droplet shape with a CCD camera, and then using image processing to determine the radius (r) and height (h) of the droplet image, which were then substituted into the following equation (θ / 2 method). θ=2arctan(h / r)

[0057] The PTFE of the present disclosure preferably has a peak temperature of not more than 348° C., more preferably not more than 346° C., and even more preferably not more than 344° 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 simultaneous differential thermal analyzer). The peak temperature is determined as the temperature corresponding to the minimum 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.

[0058] The PTFE of the present disclosure preferably has a melting point of not more than 348° C., more preferably not more than 346° C., and even more preferably not more than 344° C. The melting point is a value measured by the following method. Approximately 10 mg of powder that has not been heated above 300°C is weighed out and placed in a special aluminum pan for measurement using a TG / DTA (thermogravimetric simultaneous differential thermal analyzer). The melting point is determined by heating the aluminum pan in an air atmosphere from 25°C to 600°C at a rate of 10°C / min, and the temperature corresponding to the minimum value of the differential thermal (DTA) curve is taken as the melting point.

[0059] The PTFE of the present disclosure is preferably substantially free of fluorine-containing surfactant. In the PTFE of the present disclosure, "substantially free of fluorine-containing surfactant" means that the fluorine-containing surfactant is 10 ppm or less relative to the PTFE. The fluorine-containing surfactant content is preferably 1 ppm or less, more preferably 100 ppb or less, even more preferably 10 ppb or less, and even more preferably 1 ppb or less, and particularly preferably the fluorine-containing surfactant is below the detection limit as measured by liquid chromatography-mass spectrometry (LC / MS / MS). The amount of the fluorine-containing surfactant can be quantified by a known method. For example, it can be quantified by LC / MS / MS analysis. First, the obtained PTFE powder is extracted with an organic solvent such as methanol, and molecular weight information is extracted from the LC / MS / MS spectrum of the extract, and its agreement with the structural formula of the candidate surfactant is confirmed. Then, aqueous solutions of the confirmed surfactants at five or more levels of concentration are prepared, and LC / MS / MS analysis is performed at each concentration to create a calibration curve with the area. The obtained PTFE powder is subjected to Soxhlet extraction with methanol, and the extract is subjected to LC / MS / MS analysis for quantitative measurement. The fluorine-containing surfactant is the same as that exemplified in the production method described later. For example, it may be a surfactant containing fluorine atoms and having a total carbon number of 20 or less excluding the anionic group, a surfactant containing fluorine atoms and having a molecular weight of 800 or less in the anionic group, and a fluorine-containing surfactant having a LogPOW of 3.5 or less. The "anionic portion" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF2) represented by the formula (I) below n1 In the case of COOM, "F(CF2) n1 The "COO" part. The anionic fluorine-containing surfactants include those represented by the general formula (N 0 ) and specifically, compounds represented by the general formula (N 1 ), a compound represented by the general formula (N 2), a compound represented by the general formula (N 3 ), a compound represented by the general formula (N 4 ) and a compound represented by the general formula (N 5 ) represented by the general formula (I). More specifically, perfluorocarboxylic acid (I) represented by the general formula (I), ω-H perfluorocarboxylic acid (II) represented by the general formula (II), perfluoropolyether carboxylic acid (III) represented by the general formula (III), perfluoroalkyl alkylene carboxylic acid (IV) represented by the general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by the general formula (V), perfluoroalkyl sulfonic acid (VI) represented by the general formula (VII), ω-H perfluoro sulfonic acid (VII) represented by the general formula (VII), perfluoroalkyl alkylene sulfonic acid (VIII) represented by the general formula (VIII), alkyl alkylene carboxylic acid (IX) represented by the general formula (IX), fluorocarboxylic acid (X) represented by the general formula (X), alkoxy fluoro sulfonic acid (XI) represented by the general formula (XI), and compound (XII) represented by the general formula (XII).

[0060] The PTFE of the present disclosure is preferably heat-treated at a temperature of 240°C, and the breaking strength of an expanded bead produced under the following condition (A) measured under the following condition (X) is 29.0 N or more, and is substantially free of a fluorine-containing surfactant. Condition (A): 21.7 g of lubricant was added to 100 g of PTFE powder and mixed in a glass bottle at room temperature for 3 minutes. 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 (2.5 mm diameter, 11 mm land length, 30° entry angle) 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 inches / minute (51 cm / minute). The lubricated PTFE extrusion bead obtained by the paste extrusion is dried at 230°C for 30 minutes, and the lubricant is removed from the bead to obtain a dried PTFE extrusion bead. The dried PTFE extrusion bead is then cut to an appropriate length, clamped at each end with a clamp spacing of 1.5 inches (38 mm), and heated to 300°C in an air-circulating oven. The clamps are then separated at a rate of 1000% / second until a separation distance equivalent to 2400% is reached, and a stretch test is performed to obtain an expanded bead. This stretching method essentially follows the method disclosed in U.S. Pat. No. 4,576,869, except for the extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" refers to the increase in length due to stretching and is usually expressed relative to the original length. In the above manufacturing method, the stretch rate is 1000% / second, and the total stretch is 2400%. Condition(X): The stretched bead (produced by stretching the bead) is clamped and fixed between movable jaws with a gauge length of 5.0 cm, and a tensile test is carried out at 25°C and a speed of 300 mm / min. The strength at which it breaks is taken as the breaking strength. The lubricant is made of 100% isoparaffin hydrocarbon, with an initial boiling point of 180°C, a dry point of 188°C, a flash point of 54°C, and a density (15°C) of 0.758 g / cm 3 A lubricant having a KB (Kauri-butanol value) of 26, an aniline point of 85°C, and an aromatic content of less than 0.01% by mass can be used. Specifically, Isopar H (registered trademark) manufactured by Exxon can be used as such a lubricant.

[0061] The PTFE of the present disclosure is preferably such that the breaking strength of an expanded body produced under condition (A) by heat treatment at a temperature of 240°C, measured under condition (X), is 29.0 N or more, and the thermal instability index (TII) is 20 or more.

[0062] The PTFE of the present disclosure preferably has a breaking strength of 29.0 N or more when measured under condition (X) of an expanded body produced under condition (A). The breaking strength is more preferably 30.0 N or more, even more preferably 32.0 N or more, and even more preferably 35.0 N or more. The higher the breaking strength, the better, and there is no upper limit to the breaking strength, but it may be, for example, 80.0 N or less, or 50.0 N or less. The breaking strength is a value determined by the following method. After the above heat treatment, the stretched body produced under condition (A) is clamped and fixed between movable jaws with a gauge length of 5.0 cm, and a tensile test is carried out at 25°C and a speed of 300 mm / min. The strength at which it breaks is taken as the breaking strength.

[0063] The PTFE of the present disclosure is preferably heat-treated at a temperature of 240°C, and has a breaking strength of 22.0 N or more when measured under the condition (X) of an expanded bead produced under the condition (B) below, and is substantially free of a fluorine-containing surfactant. Condition (B): 21.7 g of lubricant was added to 100 g of PTFE powder and mixed in a glass bottle at room temperature for 3 minutes. 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 (2.5 mm diameter, 11 mm land length, 30° entry angle) 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 inches / minute (51 cm / minute). The lubricated PTFE extrusion bead obtained by the paste extrusion described above is dried at 230°C for 30 minutes, and the lubricant is removed from the bead to obtain a dried PTFE extrusion bead. The dried PTFE extrusion bead is then cut to an appropriate length, clamped at each end with a clamp spacing of 2.0 inches (51 mm), and heated to 300°C in an air-circulating oven. The clamps are then separated at 100% / second until a separation distance corresponding to a desired stretch (total stretch) of 2400% is reached, and a stretch test is performed to obtain an expanded bead. This stretching method essentially follows the method disclosed in U.S. Pat. No. 4,576,869, except for the extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" refers to the increase in length due to stretching and is usually expressed relative to the original length. Condition(X): The stretched bead (produced by stretching the bead) is clamped and fixed between movable jaws with a gauge length of 5.0 cm, and a tensile test is carried out at 25°C and a speed of 300 mm / min. The strength at which it breaks is taken as the breaking strength. The lubricant is made of 100% isoparaffin hydrocarbon, with an initial boiling point of 180°C, a dry point of 188°C, a flash point of 54°C, and a density (15°C) of 0.758 g / cm 3 A lubricant having a KB (Kauri-butanol value) of 26, an aniline point of 85°C, and an aromatic content of less than 0.01% by mass can be used. Specifically, Isopar H (registered trademark) manufactured by Exxon can be used as such a lubricant.

[0064] The PTFE of the present disclosure is preferably heat-treated at a temperature of 240°C and has an expanded body produced under condition (B) with a breaking strength of 22.0 N or more and a thermal instability index (TII) of 20 or more.

[0065] The PTFE of the present disclosure preferably has a breaking strength of 22.0 N or more when measured under condition (X) of an expanded body produced under condition (B). The breaking strength is more preferably 23.0 N or more, even more preferably 25.0 N or more, even more preferably 28.0 N or more, and particularly preferably 30.0 N or more. The higher the breaking strength, the better, and there is no upper limit to the breaking strength, but it may be, for example, 80.0 N or less, or 50.0 N or less. The breaking strength is a value determined by the following method.

[0066] The PTFE of the present disclosure preferably contains 99.0% by mass or more of PTFE and 1.0% by mass or less of components other than PTFE, more preferably 99.5% by mass or more of PTFE and 0.5% by mass or less of components other than PTFE, still more preferably 99.9% by mass or more of PTFE and 0.1% by mass or less of components other than PTFE, and particularly preferably substantially 100.0% by mass of PTFE, relative to the total mass of solids.

[0067] The PTFE of the present disclosure may be in the form of a wet powder and may contain 0.0001 to 50% by mass of an aqueous medium. The amount of the aqueous medium may be 0.0001 to 1.0% by mass, or may be 0.0001 to 0.01% by mass. The amount of the aqueous medium can be determined by the weight loss when dried at 150° C. for 60 minutes.

[0068] In the PTFE of the present disclosure, the heat treatment is carried out at 240° C. More specifically, the heat treatment is carried out at 240° C. for 18 hours. The heat treatment may be for drying the PTFE of the present disclosure. For example, when the PTFE of the present disclosure is a wet PTFE powder, the heat treatment may be for drying the moisture contained in the wet powder.

[0069] In the PTFE of the present disclosure, the production of the expanded body is preferably carried out under the above condition (A) or condition (B).

[0070] The PTFE of the present disclosure is preferably extruded at an extrusion pressure of 50.0 MPa or less, has a breaking strength of 29.0 N or more when measured under condition (X) of an expanded body produced under condition (A), and is substantially free of a fluorine-containing surfactant. The extrusion pressure is more preferably 40.0 MPa or less, more preferably 8.0 MPa or more, and even more preferably 10.0 MPa or more.

[0071] The PTFE of the present disclosure is preferably one in which the extrusion pressure is 50.0 MPa or less, the breaking strength of an expanded body produced under condition (A) measured under condition (X) is 29.0 N or more, and the thermal instability index (TII) is 20 or more. The extrusion pressure is more preferably 40.0 MPa or less, more preferably 8.0 MPa or more, and even more preferably 10.0 MPa or more.

[0072] The PTFE of the present disclosure preferably has a breaking strength of 34.0 N or more when measured under condition (X) of an expanded body produced under the above condition (A), and is substantially free of a fluorine-containing surfactant. The breaking strength is more preferably 35.0 N or more, even more preferably 37.0 N or more, and even more preferably 40.0 N or more. The higher the breaking strength, the better, but the upper limit of the breaking strength is, for example, 100.0 N.

[0073] The PTFE of the present disclosure preferably has a breaking strength of 34.0 N or more, measured under condition (X) of an expanded body produced under the above condition (A), and a thermal instability index (TII) of 20 or more. The breaking strength is more preferably 35.0 N or more, even more preferably 37.0 N or more, and even more preferably 40.0 N or more. The higher the breaking strength, the better, but the upper limit of the breaking strength is, for example, 100.0 N.

[0074] The PTFE of the present disclosure preferably has a breaking strength of 29.0 N or more when measured under condition (X) of an expanded body produced under the above condition (B), and is substantially free of a fluorine-containing surfactant. The breaking strength is more preferably 30.0 N or more, even more preferably 32.0 N or more, and even more preferably 35.0 N or more. The higher the breaking strength, the better, and there is no upper limit to the breaking strength, but it may be, for example, 100.0 N or less, or 80.0 N or less.

[0075] The PTFE of the present disclosure preferably has a breaking strength of 29.0 N or more, measured under condition (X) of an expanded body produced under condition (B) above, and a thermal instability index (TII) of 20 or more. The breaking strength is more preferably 30.0 N or more, even more preferably 32.0 N or more, and even more preferably 35.0 N or more. The higher the breaking strength, the better, and there is no upper limit to the breaking strength, but it may be, for example, 100.0 N or less, or 80.0 N or less.

[0076] The PTFE of the present disclosure is preferably expandable. In this specification, "expandable" is determined according to the following criteria. 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 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 (2.5 mm diameter, 11 mm land length, 30° entry angle) at room temperature at a reduction ratio of 100:1 to obtain a uniform bead. The extrusion speed, i.e., ram speed, was 20 in / min (51 cm / min). The bead obtained by paste extrusion was heated at 230°C for 30 minutes to remove the lubricant from the bead. The bead (extrudate) was then cut to the appropriate length, clamped at each end with a clamp spacing of 1.5 in (38 mm), and heated to 300°C in an air-circulating oven. The clamps are then separated at a desired speed (stretch rate) until a separation distance corresponding to the desired stretch (total stretch) is achieved, and a stretch test is performed. This stretching method essentially follows the method disclosed in U.S. Pat. No. 4,576,869, except for the extrusion speed (51 cm / min instead of 84 cm / min). "Stretch" is the increase in length due to drawing, and is usually expressed relative to the original length. In this production method, the stretch rate is 1000% / sec, and the total stretch is 2400%. This means that the stretch test results in a stretched bead with a uniform appearance without breakage.

[0077] The PTFE of the present disclosure preferably has an average particle size (average secondary particle size) of 100 to 2000 μm. The lower limit of the average secondary particle size is more preferably 200 μm or more, and even more preferably 300 μm or more. The upper limit of the average secondary particle size is preferably 1000 μm or less, more preferably 800 μm or less, and particularly preferably 700 μm or less. The above average particle size is a value measured in accordance with JIS K 6891.

[0078] The PTFE of the present disclosure 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 peak temperature in accordance with ASTM D-1238 and D-2116, that is, the polymer does not flow easily even in the melting temperature range.

[0079] The PTFE of the present disclosure may be a tetrafluoroethylene (TFE) homopolymer, or may be a modified PTFE obtained by copolymerizing TFE with a modifying monomer. The PTFE of the present disclosure is capable of being stretched even when it is a TFE homopolymer. The present disclosure provides a PTFE that is a TFE homopolymer and is capable of being stretched. The PTFE of the present disclosure has a higher breaking strength when it is a modified PTFE. The present disclosure provides a PTFE that is a modified PTFE and is characterized by having a breaking strength of 10.0 N or more. These PTFEs can appropriately adopt the various configurations described for the first to eighth PTFEs of the present disclosure.

[0080] The modifying monomer is not particularly limited as long as it is copolymerizable with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene (HFP), hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF), perfluorovinyl ethers, (perfluoroalkyl)ethylenes, ethylene, etc. The modifying monomer used may be one type or multiple types.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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 ...

[0085] [ka]

[0086] (wherein m represents 0 or an integer of 1 to 4), and Rf is a group represented by the following formula:

[0087] [ka]

[0088] (wherein n represents an integer of 1 to 4).

[0089] The (perfluoroalkyl)ethylene (PFAE) is not particularly limited, and examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.

[0090] A preferred example of the modifying monomer is a comonomer (3) having a monomer reactivity ratio of 0.1 to 8. The presence of the comonomer (3) makes it possible to obtain PTFE particles having a small particle size and an aqueous dispersion with high dispersion stability.

[0091] 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 a comonomer. The lower this value, the higher the reactivity of the comonomer with TFE. The monomer reactivity ratio can be calculated by copolymerizing TFE and a comonomer, determining the composition in the resulting polymer immediately after the start of copolymerization, and using the Feynman-Ross equation.

[0092] 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 comonomer 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 to atmospheric pressure. After cooling, the paraffin wax was separated to obtain an aqueous dispersion containing the product polymer. The aqueous dispersion was stirred to coagulate the product 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.

[0093] The comonomer (3) having a monomer reactivity ratio of 0.1 to 8 is preferably at least one selected from the group consisting of comonomers represented by formulas (3a) to (3d). CH2=CH-Rf 1 (3a) (In the formula, Rf1 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).

[0094] [ka] (In the formula, X 3 and X 4 is F, Cl or a methoxy group, and Y is of formula Y1 or Y2.

[0095] [ka] (In formula Y2, Z and Z′ are F or a fluorinated alkyl group having 1 to 3 carbon atoms.)

[0096] The content of comonomer (3) is preferably in the range of 0.00001 to 1.0% by mass relative to PTFE. The lower limit is more preferably 0.0001% 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, even more preferably 0.10% by mass, and particularly preferably 0.05% by mass.

[0097] 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, 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.

[0098] 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 1.0% by mass relative to PTFE. The lower limit of the total amount is more preferably 0.0001% by mass, even 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, even more preferably 0.10% by mass, even more preferably 0.08% by mass, even more preferably 0.05% by mass, and especially preferably 0.01% by mass.

[0099] 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)").

[0100] 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.

[0101] 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) is too small, the average primary particle size of the obtained PTFE may not be reduced. The amount of the modifying monomer (A) may be within the above range, but the upper limit can be set to, for example, 5000 ppm. In the above production method, the modifying monomer (A) may be added to the system during the reaction to improve the stability of the aqueous dispersion during or after the reaction.

[0102] 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.

[0103] 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.

[0104] Examples of the hydrophilic group in the modified monomer (A) include -NH, -PO, -OPO, -SO, -OSO, and -COOM (wherein M represents H, a metal atom, or NR 74. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 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 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 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.

[0105] 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.

[0106] 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).

[0107] 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.

[0108] In the polymerization, a compound having an unsaturated bond can be used as the modifying monomer (A).

[0109] 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 2are 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 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. ) are examples of the hydrophilic group. Of these, -SO3M or -COOM is preferred. R 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 may be a monovalent or divalent metal atom, such as an alkali metal (Group 1) or an alkaline earth metal (Group 2), with Na, K, or Li being preferred. By using the modifying monomer (A), 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.

[0110] 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.

[0111] 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 a Examples 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.

[0112] R ais 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.

[0113] R a Specific 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.

[0114] -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.

[0115] 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.

[0116] 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.

[0117] -R in the above general formula (4) a -CZ 1 Z 2 - 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 - 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.

[0118] 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.

[0119] 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.

[0120] 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, Y 3 is a hydrophilic group, and Rf 0is a perfluorinated divalent linking group which may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and which optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0121] 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).

[0122] In general formula (4), Y 3 One of the preferred embodiments is -OSO3M. 3 is -OSO3M, the polymerized units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2CH2OSO3M)]-, -[CH2CH((CF2)4CH2OSO3M)]-, -[CF2CF(O(CF2)4CH2OSO3M)]-, -[CF2CF(OCF2CF(CF3)CH2OSO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CH 2OSO3M)]-, -[CH2CH((CF2)4CH2OSO3M)]-, -[CF2CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M)]-, -[CH2CH(CF2CF2CH2OSO3M)]-, -[CF2CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M)]-, -[CH2CH(CF2CF2CH2OSO3M)]-, etc. In the above formula, M is the same as above.

[0123] In general formula (4), Y 3 Another preferred form is -SO3M. 3is -SO3M, examples of polymerized units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2SO3M)]-, -[CF2CF(O(CF2)4SO3M)]-, -[CF2CF(OCF2CF(CF3)SO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M)]-, -[CH2CH((CF2)4SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, -[CH2CH(CF2CF2SO3M)]-, and the like. In the above formulas, M is the same as above.

[0124] In general formula (4), Y 3 -COOM is also a preferred form. 3 is -COOM, the polymerized units based on the compound represented by general formula (4) include -[CFCF(OCFCFCOOM)]-, -[CFCF(O(CF)COOM)]-, -[CFCF(OCFCF(CF)COOM)]-, -[CFCF(OCFCF(CF)O(CF) n COOM)]-(n is greater than 1), -[CH2CH(CF2CF2COOM)]-, -[CH2CH((CF2)4COOM)]-, -[CH2CH(CF2CF2COOM)]-, -[CH2CH((CF2)4COOM)]-, -[CF2CF(OCF2CF2SO2NR'CH2COOM)]-, -[CF2CF(O(CF2)4SO2NR'CH2COOM)]-, -[CF2CF(OCF2CF(CF3)SO2NR'CH2COOM)]-, -[CF2CF( OCF2CF(CF3)OCF2CF2SO2NR'CH2COOM)]-, -[CH2CH(CF2CF2SO2NR'CH2COOM)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR'CH2COOM)]-, -[CH2CH((CF2)4SO2NR'CH2COOM)]-, -[CH2CH(CF2CF2SO2NR'CH2COOM)]-, -[CH2CH((CF2)4SO2NR'CH2COOM)]-, etc. In the above formula, R' represents H or C1-4 is an alkyl group, and M is the same as above.

[0125] In general formula (4), Y 3 In another preferred embodiment, Y is -OPO3M. 3 is -OPO3M, examples of the polymerized units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2CH2OP(O)(OM)2)]-, -[CF2CF(O(CF2)4CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF2SO2N(C H3)CH2CH2OP(O)(OM)2)]-, -[CF2CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2)]-, -[CH2CH(CF2CF2CH2OP(O)(OM)2)]-, -[CH2CH((CF2)4CH2OP(O)(OM)2)]-, -[CH2CH(CF2CF2CH2OP(O)(OM)2)]-, -[CH2CH((CF2)4CH2OP(O)(OM)2)]-, etc. In the above formula, M is the same as above.

[0126] In general formula (4), Y 3 In another preferred embodiment, Y is -PO3M. 3 is -PO3M, examples of the polymerized units based on the compound represented by general formula (4) include -[CF2CF(OCF2CF2P(O)(OM)2)]-, -[CF2CF(O(CF2)4P(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)P(O)(OM)2)]-, -[CF2CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2)]-, -[CH2CH(CF2CF2P(O)(OM)2)]-, -[CH2CH((CF2)4P(O)(OM)2)]-, -[CH2CH(CF2CF2P(O)(OM)2)]-, and -[CH2CH((CF2)4P(O)(OM)2)]-, where M is the same as above.

[0127] 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; 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:

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more, and more preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less. For example, the following formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 are H or F;Z respectively 4 is H, F, or CF3; p1+q1+r1 are integers from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, except for Z 3 and Z 4 are both H, it is also preferable that p1+q1+r1+s1 is not 0). Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)- (wherein n is an integer of 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples thereof include -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF2CF2O-CF2CH2-, -CF(CF3)CH2-, and the like. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0134] In the above general formula (5), Y 3 is -COOM, -SO3M or -OSO3M (M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 are H or organic groups and may be the same or different. Any two of them may be bonded to each other to form a ring. R 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. The above M is —H, a metal atom, or —NR 7 4 is preferred, and -H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or -NR 7 4 is more preferred, -H, -Na, -K, -Li or -NH4 is even more preferred, -Na, -K or -NH4 is even more preferred, -Na or -NH4 is especially preferred, and -NH4 is most preferred. Above Y 3 As the alkyl group, -COOM or -SO3M is preferred, and -COOM is more preferred.

[0135] Examples of the monomer represented by general formula (5) include the following formula (5a): CX h 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5a) (In the formula, each h are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, and Y 3 is the same as defined above. ) is a suitable example of a fluoroallyl ether compound. In the general formula (5a), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in that PTFE particles having a small primary particle size can be obtained. 3 is preferably -COOM in that it provides suitable water solubility and surface activity, and the above M is preferably H or NH4 in that it is less likely to remain as an impurity and the heat resistance of the resulting composition and the stretched body obtained from the composition is improved.

[0136] The monomer represented by the general formula (5) is preferably a monomer (5b) represented by the following general formula (5b). CH2=CF(-CF2-O-Rf-Y 3 ) (5b) (Wherein Rf and Y 3 is the same as above.)

[0137] Specific examples of the monomer represented by general formula (5b) include the monomer represented by the following formula:

[0138] [ka]

[0139] (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,

[0140] [ka]

[0141] Among them,

[0142] [ka]

[0143] It is preferable that:

[0144] The monomer represented by the general formula (5b) 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.

[0145] The monomer represented by the general formula (5) is preferably a monomer (5c) represented by the following general formula (5c). CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5c) (In the formula, each 2 are the same and represent F or H. n5 represents 0 or an integer of 1 to 10, and Y 3 is the same as the definition above.)

[0146] In the formula (5c), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in terms of the stability of the resulting aqueous dispersion. 3 -COOM is advantageous in that it provides moderate water solubility and stability of aqueous dispersion. 1 It is preferable that the above M 1 is preferably H or NH4, since it is unlikely to remain as an impurity and the heat resistance of the resulting molded article is improved.

[0147] Examples of the perfluorovinyl alkyl compound represented by the formula (5c) 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.

[0148] Furthermore, examples of the monomer represented by general formula (5) include a monomer represented by the following general formula (5d) and a monomer represented by the following general formula (5e).

[0149] CF2=CFCF2-O-Rf-Y 3 (5d) CF2=CF-Rf-Y 3 (5e) (Wherein Rf and Y 3 is the same as above)

[0150] More specifically, [ka] etc.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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. 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.

[0155] The monomer represented by the above general formula (6) is preferably at least one selected from the group consisting of monomers represented by the following general formulae (6a), (6b), (6c) and (6d). CF2=CF-(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 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 represents H or an organic group. CF2=CF-(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, X1 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.)

[0156] 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.

[0157] The perfluorovinyl alkyl compound represented by the above formula (6a) is, for example, CF2=CFCF2COOM 1 (In the formula, M 1 is the same as the definition above.

[0158] 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.

[0159] 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 1is preferably H or NH4 in terms of improving dispersion stability.

[0160] 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.

[0161] Examples of the perfluorovinyl ether compound represented by the above formula (6d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM 1 (In the formula, M 1 represents H, NH4 or an alkali metal.

[0162] 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.

[0163] 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 1 is preferred, and M 1is H, metal atom, NR 7 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. 7 represents H or an organic group.

[0164] 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.

[0165] 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.

[0166] 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).

[0167] The content of the modifying monomer (A) is preferably in the range of 0.00001 to 1.0% by mass. The lower limit is more preferably 0.0001% by mass, even 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, even more preferably 0.10% by mass, even more preferably 0.08% by mass, especially preferably 0.05% by mass, and especially especially preferably 0.01% by mass.

[0168] The modified monomer is preferably at least one selected from the group consisting of hexafluoropropylene, vinylidene fluoride, fluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, and ethylene, since a high-strength stretched product can be obtained; more preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), (perfluorobutyl)ethylene, (perfluorohexyl)ethylene, and (perfluorooctyl)ethylene; and even more preferably perfluoro(methyl vinyl ether).

[0169] The modified PTFE preferably contains the modified monomer unit in the range of 0.00001 to 1.0% by mass. The lower limit of the modified monomer unit is more preferably 0.0001% by mass, even more preferably 0.0005% by mass, even more preferably 0.001% by mass, still more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit of the modified monomer unit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.30% by mass, even more preferably 0.10% by mass, even more preferably 0.08% by mass, even more preferably 0.05% by mass, and especially particularly preferably 0.01% by mass. In this specification, the modified monomer unit refers to a portion of the molecular structure of the modified PTFE that is derived from the modified monomer, and the total monomer units refers to portions derived from all monomers in the molecular structure of the modified PTFE.

[0170] 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.

[0171] The PTFE is preferably a PTFE that has no history of being heated at a temperature equal to or higher than the first peak temperature. The PTFE may be unsintered or semi-sintered. From the viewpoint of a simple process or ease of controlling the thickness and pore size, unsintered PTFE is preferred. From the viewpoint of increasing the strength of the biaxially stretched membrane or reducing the pore size, semi-sintered PTFE is preferred. An example of unsintered PTFE is PTFE after polymerization. The unsintered PTFE is PTFE that has no history of being heated to a temperature equal to or higher than the secondary peak temperature, and the semi-sintered PTFE is PTFE that has no history of being heated to a temperature equal to or higher than the primary peak temperature, and is PTFE that has been heated to a temperature equal to or lower than the primary peak temperature and equal to or higher than the secondary peak temperature. The primary peak temperature means the maximum peak temperature of the endothermic curve appearing on the crystalline melting curve when unsintered PTFE is measured by a differential scanning calorimeter. The second peak temperature means the maximum peak temperature of the endothermic curve that appears on the crystalline melting curve when PTFE heated to a temperature equal to or higher than the first peak temperature (for example, 360°C) is measured with a differential scanning calorimeter. In this specification, the endothermic curve was obtained by using a differential scanning calorimeter and raising the temperature at a rate of 10° C. / min.

[0172] The PTFE may have a core-shell structure. Examples of polytetrafluoroethylene having a core-shell structure include modified polytetrafluoroethylene particles containing a core of high-molecular-weight polytetrafluoroethylene and a shell of lower-molecular-weight polytetrafluoroethylene or modified polytetrafluoroethylene. An example of such modified polytetrafluoroethylene is the polytetrafluoroethylene described in JP-A-2005-527652.

[0173] The PTFE of the present disclosure can be obtained by a production method including a step of emulsion polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modified monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of a specific hydrocarbon surfactant, and a step of continuously adding the specific hydrocarbon surfactant in the above step.The PTFE of the present disclosure is preferably obtained by the above production method. The continuous addition of a specific hydrocarbon surfactant means, for example, adding the specific hydrocarbon surfactant over time, without interruption, or in portions, rather than all at once. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) that has been subjected to radical treatment or oxidation treatment. 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, the radical treatment may involve adding deionized water and a hydrocarbon surfactant to a reactor, sealing the reactor, replacing the system with nitrogen, heating and pressurizing the reactor, adding a polymerization initiator, stirring for a certain period of time, and then depressurizing the reactor to atmospheric pressure and 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. The PTFE of the present disclosure, obtained by such a production method, can have an SSG of 2.175 or less and exhibit excellent stretchability, even when obtained in the presence of a hydrocarbon surfactant. In other words, surprisingly, the production method using a specific hydrocarbon surfactant makes it possible to produce PTFE having a molecular weight equivalent to that produced by a production method using a conventional fluorine-containing surfactant, even without using a conventional fluorine-containing surfactant.

[0174] The present disclosure also provides polytetrafluoroethylene obtained by a production method comprising the steps of: carrying out emulsion polymerization of tetrafluoroethylene alone, or emulsion polymerization of tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene, in an aqueous medium in the presence of a specific hydrocarbon surfactant; and continuously adding the specific hydrocarbon surfactant during the above step.

[0175] In the above-mentioned production method, the step of continuously adding the specific hydrocarbon surfactant preferably starts adding the hydrocarbon surfactant to the aqueous medium when the solid content of the PTFE formed in the aqueous medium is less than 0.60% by mass. It is preferable to start adding the specific hydrocarbon surfactant to the aqueous medium when the solid content is 0.5% by mass or less. It is more preferable to start adding the specific hydrocarbon surfactant when the solid content is 0.3% by mass or less, even more preferably when it is 0.2% by mass or less, even more preferably when it is 0.1% by mass or less, and it is particularly preferable to start adding it together with the initiation of polymerization. The solid content is the concentration relative to the total of the aqueous medium and the PTFE.

[0176] 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.

[0177] In a process in which emulsion polymerization of tetrafluoroethylene alone or emulsion polymerization of tetrafluoroethylene and a modified monomer copolymerizable with tetrafluoroethylene is carried out in an aqueous medium in the presence of the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant is preferably large, preferably 0.0001 to 10% by mass relative to 100% by mass of the aqueous medium. A more preferred lower limit is 0.001% by mass, and a more preferred upper limit is 1% by mass. If the amount is less than 0.0001% by mass, the dispersing power may be insufficient, while if the amount exceeds 10% by mass, the effect commensurate with the amount may not be obtained, and instead, the polymerization rate may decrease or the reaction may stop. The amount of the specific hydrocarbon surfactant is determined appropriately depending on the type of monomer used, the molecular weight of the target PTFE, and other factors.

[0178] The specific hydrocarbon surfactants include those represented by the formula: RX (wherein R is 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 is -OSOX 1 , -COOX 1 or -SO3X 1 (X 1 is H, metal atom, NR 1 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 1 is H or an organic group, and may be the same or different. )) is preferred. 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. The specific hydrocarbon surfactant is 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 R 4a are H or organic groups, and may be the same or different. 1a , R 2a and R 3aAny 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 1cR 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.) 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 -COOX d (X d is H, metal atom, NR 5d4. 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 and a surfactant (d) represented by the following formula (e): [ka] (In the formula, R 1e ~R 5e represents H or a monovalent substituent, provided that R 1e and R 3e At least one of the groups has the general formula: -Y e -R 6e a group represented by R 2e and R 5e At least one of the groups has the general formula: -X e -A e or a group represented by the general formula: -Y e -R 6e represents a group represented by the following formula: Also, X e is the same or different in each occurrence and is a divalent linking group or bond; A e may be the same or different in each occurrence, -COOM e , -SO3M e or -OSO3M e (Me is H, metal atom, NR 7e 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7e is H or an organic group); Y e are the same or different in each occurrence, and are -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e - and -NR 8e a divalent linking group selected from the group consisting of CO—, or a bond, R 8e is H or an organic group; R 6e are 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 1e ~R 5e Any two of the groups may be bonded to each other to form a ring.)

[0179] The surfactant (a) will now be described.

[0180] 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. 1aIn 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.

[0181] 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.

[0182] 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.

[0183] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group. R 2a and R 3a are preferably independently a single bond, a linear or branched alkylene group having one or more carbon atoms, or a cyclic alkylene group having three or more carbon atoms. R 2a and R 3a The alkylene group constituting the formula (I) preferably does not contain a carbonyl group.

[0184] 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.

[0185] 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.

[0186] 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. 4ais 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 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.

[0187] 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.

[0188] Also, R 1a The formula is as follows: [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 12a may be the same or different. ) is more preferred.

[0189] n 11ais 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.

[0190] 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.

[0191] 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 12a 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 104a (In the formula, R 104a is an alkyl group). R 12a The alkylene 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 alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0192] 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-).

[0193] Examples of surfactant (a) include the following surfactants: a is as described above.

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] The surfactant (a) is a novel compound and can be produced, for example, by the production method exemplified below.

[0203] 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.

[0204] 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.

[0205] 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).

[0206] Ea 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.

[0207] R 21a is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0208] Examples of the chlorosilane compound include: [ka] Examples include:

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] The reaction in step (12a) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0215] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

[0216] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0217] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0218] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0219] 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.

[0220] The reaction temperature in step (12a) is preferably 40 to 60°C, more preferably 50 to 55°C.

[0221] The reaction pressure in step (12a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0222] The reaction time in step (12a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0223] 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).

[0224] 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.

[0225] 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.

[0226] The reaction temperature in step (13a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0227] The reaction pressure in step (13a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0228] The reaction time in step (13a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] The reaction temperature in step (14a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0236] The reaction pressure in step (14a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0237] The reaction time in step (14a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0238] 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.

[0239] 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.

[0240] 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.)

[0241] 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.

[0242] 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.

[0243] 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.

[0244] The reaction in step (21a) can be carried out in a solvent in the presence of a base.

[0245] Examples of the base include sodium amide, sodium hydride, sodium methoxide, and sodium ethoxide.

[0246] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0247] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0248] 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.

[0249] The reaction temperature in step (21a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0250] The reaction pressure in the step (21a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0251] The reaction time in step (21a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0252] 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).

[0253] 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.

[0254] 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.

[0255] The reaction temperature in step (22a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0256] The reaction pressure in the step (22a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0257] The reaction time in step (22a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] 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.

[0264] The reaction temperature in step (23a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0265] The reaction pressure in the step (23a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0266] The reaction time in step (23a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0267] 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.

[0268] 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.

[0269] 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.) Compound (31a) is oxidized to give a compound of 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] The reaction in step (31a) can be carried out in a solvent, preferably hexane.

[0274] The reaction temperature in step (31a) is preferably from -100 to -40°C, more preferably from -80 to -50°C.

[0275] The reaction pressure in the step (31a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0276] The reaction time in step (31a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0277] 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.

[0278] 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.

[0279] The reaction temperature in step (32a) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0280] The reaction pressure in the step (32a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0281] The reaction time in step (32a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0282] 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).

[0283] 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.

[0284] 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.

[0285] The reaction temperature in step (33a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0286] The reaction pressure in the step (33a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0287] The reaction time in step (33a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0288] 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.

[0289] 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.

[0290] 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.

[0291] 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.

[0292] 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.

[0293] 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.

[0294] The reaction temperature in step (34a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0295] The reaction pressure in the step (34a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0296] The reaction time in step (34a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0297] 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.

[0298] 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.

[0299] 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.)

[0300] 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.

[0301] R 21a is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0302] 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.

[0303] The reaction in step (41a) is preferably carried out in the presence of a metal catalyst, such as ruthenium.

[0304] 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.

[0305] The reaction in step (41a) can be carried out in a polar solvent, preferably water, acetonitrile, dimethylacetamide, or dimethylformamide.

[0306] The reaction temperature in step (41a) is preferably 20 to 160°C, more preferably 40 to 140°C.

[0307] The reaction pressure in the step (41a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0308] The reaction time in step (41a) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0309] 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.

[0310] 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.

[0311] 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.

[0312] 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.

[0313] 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.

[0314] 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.

[0315] The reaction temperature in step (42a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0316] The reaction pressure in the step (42a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0317] The reaction time in step (42a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0318] 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.

[0319] 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.

[0320] Next, the surfactant (b) will be described.

[0321] 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.

[0322] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] In formula (b), R 2b and R 4b are independently H or a substituent. 2b and R 4b may be the same or different.

[0327] 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.

[0328] R 2b and R 4b 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.

[0329] 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).

[0330] 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.

[0331] 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.

[0332] 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.

[0333] 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-).

[0334] 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.

[0335] 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.

[0336] 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.

[0337] 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.

[0338] 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 alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are 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.

[0339] 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

[0340] L is preferably a single bond.

[0341] 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.

[0342] 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.

[0343] 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.

[0344] 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.

[0345] The above integral value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

[0346] 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.

[0347] The surfactant (b) is a novel compound and can be produced, for example, by the production method exemplified below.

[0348] 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.

[0349] 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.

[0350] 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.

[0351] 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).

[0352] 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).

[0353] In the method (1), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (10b).

[0354] 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.

[0355] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0356] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0357] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0358] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0359] 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.

[0360] The reaction temperature in the method (1) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0361] The reaction pressure in the method (1) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0362] The reaction time in the method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0363] In the method (2), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per mole of compound (10b).

[0364] 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.

[0365] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0366] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0367] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0368] The temperature for the reaction of compound (10b) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0369] 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.

[0370] The reaction time of compound (10b) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0371] 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.

[0372] The oxidation in method (2) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0373] The oxidation temperature in the method (2) is preferably 0 to 100°C, more preferably 0 to 80°C.

[0374] The oxidation pressure in the method (2) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0375] The oxidation time in method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0376] 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 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).

[0377] 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.

[0378] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0379] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0380] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0381] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0382] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0383] The oxidation temperature in step (12b) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0384] The oxidation pressure in the step (12b) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0385] The oxidation time in step (12b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0386] 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 mol of compound (12b).

[0387] 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.

[0388] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0389] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0390] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0391] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0392] The temperature for sulfonation in step (13b) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0393] The pressure for sulfonation in step (13b) is preferably 0 to 10 MPa, more preferably 0.1 to 5 MPa.

[0394] The time for sulfate esterification in step (13b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0395] 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.

[0396] R 101b is preferably an alkyl group having 1 to 20 carbon atoms. 101b may be the same or different.

[0397] The ozonolysis in step (21b) can be carried out by reacting compound (20b) with ozone, followed by post-treatment with a reducing agent.

[0398] Ozone can be generated by silent electrical discharge in oxygen gas.

[0399] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0400] 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.

[0401] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0402] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0403] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0404] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0405] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0406] The temperature for ozonolysis in step (21b) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0407] The pressure for ozonolysis in step (21b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0408] The time for ozonolysis in step (21b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0409] 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.

[0410] 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.

[0411] 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.

[0412] 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.

[0413] 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.

[0414] 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.

[0415] 2 R's 22b may be the same or different.

[0416] R 21b and R 22bPreferably, the total number of carbon atoms is 1 to 7, more preferably 1 or 2, and most preferably 1.

[0417] The epoxidation in step (31b) can be carried out by reacting compound (30b) with an epoxidizing agent.

[0418] 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).

[0419] 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.

[0420] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0421] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0422] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0423] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0424] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0425] 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.

[0426] The epoxidation temperature in step (31b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0427] The pressure for epoxidation in step (31b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0428] The epoxidation time in step (31b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0429] 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).

[0430] 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.

[0431] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0432] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0433] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0434] The reaction temperature in step (32b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0435] The reaction pressure in step (32b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0436] The reaction time in step (32b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0437] 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).

[0438] 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.

[0439] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0440] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

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

[0446] The oxidation pressure in the step (33b) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0447] The oxidation time in step (33b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0448] 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.

[0449] 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.

[0450] 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.

[0451] 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).

[0452] The water can be used in an amount of 0.5 to 1000 moles per mole of compound (10b).

[0453] 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).

[0454] 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.

[0455] 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.

[0456] 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.

[0457] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0458] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0459] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0460] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0461] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0462] 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.

[0463] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0464] The oxidation temperature in step (41b) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0465] The oxidation pressure in the step (41b) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0466] The oxidation time in step (41b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0467] 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.

[0468] 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.) 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 (51b) 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 (52b) is oxidized to give a compound of the following formula: [ka] (In the formula, L, R 2b , R 3b , R 11b and n are as defined above.), and The compound (53b) 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 (54b) of obtaining a compound (54b) represented by the formula (54b) as described above.

[0469] Z 51b is preferably F, Cl, Br or I, and more preferably Br.

[0470] Examples of the halogenating agent used in step (51b) include N-bromosuccinimide and N-chlorosuccinimide. The halogenating agent can be used in an amount of 0.5 to 10.0 moles per mole of compound (50b).

[0471] The reaction in step (51b) 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 (50b).

[0472] The reaction in step (51b) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0473] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0474] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0475] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0476] The reaction temperature in step (51b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0477] The reaction pressure in the step (51b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0478] The reaction time in step (51b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0479] In the step (52b), the alkylene glycol can be used in an amount of 0.5 to 10.0 moles per mole of the compound (51b).

[0480] The reaction in step (52b) 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 (51b).

[0481] The reaction in step (52b) 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.

[0482] 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.

[0483] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0484] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0485] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0486] The reaction temperature in step (52b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0487] The reaction pressure in the step (52b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0488] The reaction time in step (52b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0489] The oxidation in step (53b) can be carried out by reacting compound (52b) with an oxidizing agent in the presence of water and a palladium compound, and the same conditions as those for the oxidation in step (41b) can be used.

[0490] The sulfate esterification in step (54b) can be carried out by reacting compound (53b) with a sulfating reagent, and the same conditions as those for the sulfate esterification in step (13b) can be used.

[0491] 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.

[0492] Among the methods for producing the surfactant (b), a production method including the above steps (41b) and (42b) is preferred.

[0493] The surfactant (c) will now be explained.

[0494] 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.

[0495] 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.

[0496] 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.

[0497] 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.

[0498] 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.

[0499] 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.

[0500] 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. Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. 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.

[0501] 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.

[0502] Also, R 1c The formula is as follows: [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.

[0503] n 11cis 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.

[0504] 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.

[0505] 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, 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.

[0506] 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-).

[0507] Examples of the surfactant (c) include the following surfactants: c is as described above.

[0508] [ka]

[0509] [ka]

[0510] [ka]

[0511] [ka]

[0512] [ka]

[0513] [ka]

[0514] [ka]

[0515] [ka]

[0516] The surfactant (c) is a novel compound and can be produced, for example, by the production method exemplified below.

[0517] 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:

[0518] 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.

[0519] 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).

[0520] 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.

[0521] R 21c is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0522] Examples of the chlorosilane compound include: [ka] Examples include:

[0523] 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.

[0524] 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.

[0525] 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.

[0526] 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.

[0527] 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.

[0528] The reaction in step (12c) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0529] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

[0530] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0531] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an alcohol or an ether.

[0532] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0533] 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.

[0534] The reaction temperature in step (12c) is preferably 40 to 60°C, more preferably 50 to 55°C.

[0535] The reaction pressure in step (12c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0536] The reaction time in step (12c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0537] 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).

[0538] 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.

[0539] 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.

[0540] The reaction temperature in step (13c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0541] The reaction pressure in step (13c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0542] The reaction time in step (13c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0543] The oxidation in step (14c) can be carried out in a solvent in the presence of sodium chlorite.

[0544] 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.

[0545] 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.

[0546] 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.

[0547] 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.) to obtain a compound (23c) represented by the formula (23c), It can be suitably produced by a production method including the steps of:

[0548] 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.

[0549] 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.

[0550] 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.

[0551] The reaction in step (21c) can be carried out in a solvent in the presence of a base.

[0552] Examples of the base include sodium amide, sodium hydride, sodium methoxide, and sodium ethoxide.

[0553] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0554] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0555] 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.

[0556] The reaction temperature in step (21c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0557] The reaction pressure in the step (21c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0558] The reaction time in step (21c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0559] 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).

[0560] 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.

[0561] 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.

[0562] The reaction temperature in step (22c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0563] The reaction pressure in step (22c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0564] The reaction time in step (22c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0565] The oxidation in step (23c) can be carried out in a solvent in the presence of sodium chlorite.

[0566] The solvent may be alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0567] 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.

[0568] 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.

[0569] 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:

[0570] 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.

[0571] 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.

[0572] 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.

[0573] The reaction in step (31c) can be carried out in a solvent, preferably hexane.

[0574] The reaction temperature in step (31c) is preferably from -100 to -40°C, more preferably from -80 to -50°C.

[0575] The reaction pressure in the step (31c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0576] The reaction time in step (31c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0577] 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.

[0578] 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.

[0579] The reaction temperature in step (32c) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0580] The reaction pressure in step (32c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0581] The reaction time in step (32c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0582] 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 borofluoride (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0583] 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.

[0584] 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.

[0585] The reaction temperature in step (33c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0586] The reaction pressure in the step (33c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0587] The reaction time in step (33c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0588] The oxidation in step (34c) can be carried out in a solvent in the presence of sodium chlorite.

[0589] The solvent may be alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0590] 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.

[0591] 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.

[0592] 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] Step (52c) of obtaining a compound (52c) represented by Compound (52c) is heated in the presence of an acid to obtain a compound of 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:

[0593] 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.

[0594] 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.

[0595] 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.

[0596] The reaction in step (51c) can be carried out in a polar solvent, preferably water or acetonitrile.

[0597] The reaction temperature in step (51c) is preferably 20 to 100°C, more preferably 40 to 100°C.

[0598] The reaction pressure in the step (51c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0599] The reaction time in step (51c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0600] 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.

[0601] 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.

[0602] 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.

[0603] The reaction in step (52c) can be carried out in a polar solvent, preferably water.

[0604] The reaction temperature in step (52c) is preferably 20 to 100°C, more preferably 40 to 100°C.

[0605] The reaction pressure in the step (52c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0606] The reaction time in step (52c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0607] In step (53c), compound (52c) is heated in the presence of an acid to open the furan ring.

[0608] The acid is preferably hydrochloric acid or sulfuric acid.

[0609] The reaction in step (53c) can be carried out in a polar solvent, preferably water.

[0610] The reaction temperature in step (53c) is preferably 50 to 100°C, more preferably 70 to 100°C.

[0611] The reaction pressure in the step (53c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0612] The reaction time in step (53c) is preferably 0.1 to 72 hours, more preferably 1 to 12 hours.

[0613] The oxidation in step (54c) can be carried out in a solvent in the presence of sodium chlorite.

[0614] The solvent may be tert-butyl alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0615] 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.

[0616] 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.

[0617] 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:

[0618] 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.

[0619] R 21c is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0620] 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.

[0621] The reaction in step (61c) is preferably carried out in the presence of a metal catalyst, such as ruthenium.

[0622] 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.

[0623] The reaction in step (61c) can be carried out in a polar solvent, preferably water, acetonitrile, dimethylacetamide, or dimethylformamide.

[0624] The reaction temperature in step (61c) is preferably 20 to 160°C, more preferably 40 to 140°C.

[0625] The reaction pressure in the step (61c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0626] The reaction time in step (61c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0627] 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.

[0628] 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.

[0629] The reaction in step (62c) can be carried out in a polar solvent, preferably water.

[0630] The reaction temperature in step (62c) is preferably 0 to 100°C, more preferably 20 to 100°C.

[0631] The reaction pressure in the step (62c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0632] The reaction time in step (62c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0633] 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.

[0634] 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.

[0635] The surfactant (d) will now be described.

[0636] 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.

[0637] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0638] 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.

[0639] 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.

[0640] 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.

[0641] In formula (d), R 2d and R 4d are independently H or a substituent. 2d and R 4d may be the same or different.

[0642] 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.

[0643] R 2d and R 4d 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.

[0644] 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).

[0645] 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.

[0646] 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.

[0647] 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.

[0648] 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-).

[0649] R 1d , R 2d , R 3d and R 4d Any two of these may be bonded to each other to form a ring.

[0650] 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.

[0651] 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.

[0652] 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.

[0653] 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 alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li are 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.

[0654] 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

[0655] L is preferably a single bond.

[0656] 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.

[0657] 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.

[0658] 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.

[0659] The above integral value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

[0660] 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)CH2CH2CH2CH2CH2CH2CH2CH2C(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.

[0661] The surfactant (d) is a novel compound and can be produced, for example, by the production method exemplified below.

[0662] 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:

[0663] 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).

[0664] 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.

[0665] The reaction temperature in step (11d) is preferably from -78 to 150°C, more preferably from -20 to 100°C.

[0666] The reaction pressure in the step (11d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0667] The reaction time in step (11d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0668] 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:

[0669] The oxidation in step (21d) can be carried out by reacting compound (20d) with a nitrosating agent.

[0670] As the nitrosating agent, sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite, etc. can be used.

[0671] The nitrosating agent can be used in an amount of 0.5 to 10 moles per mole of compound (20d).

[0672] The oxidation in step (21d) can be carried out in a solvent, such as trifluoroacetic acid or acetonitrile.

[0673] The oxidation temperature in step (21d) is preferably from -78 to 200°C, more preferably from -20 to 100°C.

[0674] The oxidation pressure in the step (21d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0675] The oxidation time in step (21d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 24 hours.

[0676] Compound (10d) and compound (20d) are compounds 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, 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.

[0677] 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.

[0678] 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.

[0679] 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).

[0680] 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).

[0681] In the method (1d), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (100d).

[0682] 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.

[0683] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0684] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0685] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0686] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0687] 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.

[0688] The reaction temperature in the method (1d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0689] The reaction pressure in the method (1d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0690] The reaction time in the method (1d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0691] In the method (2d), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per mole of compound (100d).

[0692] 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.

[0693] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0694] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0695] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0696] The temperature for the reaction of compound (100d) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0697] 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.

[0698] The reaction time of compound (100d) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0699] 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.

[0700] The oxidation in the method (2d) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0701] The oxidation temperature in the method (2d) is preferably 0 to 100°C, more preferably 0 to 80°C.

[0702] The oxidation pressure in the method (2d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0703] The oxidation time in the method (2d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0704] 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).

[0705] 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.

[0706] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0707] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0708] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0709] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0710] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0711] The oxidation temperature in the step (102d) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0712] The oxidation pressure in the step (102d) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0713] The oxidation time in step (102d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0714] 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.

[0715] R 101d is preferably an alkyl group having 1 to 20 carbon atoms. 101d may be the same or different.

[0716] The ozonolysis in step (201d) can be carried out by reacting compound (200d) with ozone, followed by post-treatment with a reducing agent.

[0717] Ozone can be generated by silent electrical discharge in oxygen gas.

[0718] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0719] 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.

[0720] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0721] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0722] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0723] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0724] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0725] The temperature for ozonolysis in the step (201d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0726] The pressure for ozonolysis in the step (201d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0727] The time for ozonolysis in the step (201d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0728] 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.

[0729] 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.

[0730] 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.

[0731] 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.

[0732] 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.

[0733] 2 R's 22d may be the same or different.

[0734] 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.

[0735] The epoxidation in step (301d) can be carried out by reacting compound (300d) with an epoxidizing agent.

[0736] 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).

[0737] 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.

[0738] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0739] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0740] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0741] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0742] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0743] 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.

[0744] The epoxidation temperature in the step (301d) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0745] The pressure for epoxidation in the step (301d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0746] The epoxidation time in the step (301d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0747] 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).

[0748] 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.

[0749] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0750] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0751] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0752] The reaction temperature in step (302d) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0753] The reaction pressure in step (302d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0754] The reaction time in step (302d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0755] 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).

[0756] 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.

[0757] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0758] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0759] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0760] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0761] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0762] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0763] The oxidation temperature in step (303d) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0764] The oxidation pressure in the step (303d) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0765] The oxidation time in step (303d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0766] 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.

[0767] 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.

[0768] 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).

[0769] The water can be used in an amount of 0.5 to 1000 moles per mole of compound (100d).

[0770] 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).

[0771] 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.

[0772] 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.

[0773] 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.

[0774] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0775] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0776] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0777] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0778] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0779] 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.

[0780] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0781] The oxidation temperature in the step (401d) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0782] The oxidation pressure in the step (401d) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0783] The oxidation time in the step (401d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0784] 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.

[0785] 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.

[0786] 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.

[0787] The surfactant (e) will now be explained.

[0788] In formula (e), R 1e ~R 5e represents H or a monovalent substituent, provided that R 1e and R 3e At least one of the groups has the general formula: -Y e -R 6e a group represented by R 2e and R 5e At least one of the groups has the general formula: -X e -A e or a group represented by the general formula: -Y e -R 6e R represents a group represented by 1e ~R 5e Any two of these may be bonded to each other to form a ring.

[0789] R 1e 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.

[0790] R 1e 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.

[0791] R 1e 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.

[0792] The monovalent substituent includes a group represented by the general formula: -Y e -R 6e a group represented by the general formula: -X e -A e a group represented by the formula: -H, optionally substituted C 1-20 Alkyl groups, -NH2, -NHR 9e (R 9e is an organic group), -OH, -COOR 9e (R 9e is an organic group) or -OR 9e (R 9e is an organic group). The alkyl group preferably has 1 to 10 carbon atoms.

[0793] R 9e As for C 1-10 or C 1-10 The alkylcarbonyl group of C is preferred. 1-4 or C 1-4The alkylcarbonyl group of the formula is more preferred.

[0794] In the formula, X e represents, the same or different in each occurrence, a divalent linking group or bond. R 6e does not contain any of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X e is preferably a divalent linking group containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0795] X e Examples include -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, and -CONR 8e - and -NR 8e 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 8e represents H or an organic group.

[0796] R 8e The organic group in R is preferably an alkyl group. 8e 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.

[0797] In formula (e), A e may be the same or different in each occurrence, -COOM e , -SO3M e or -OSO3M e (M e is H, metal atom, NR 7e 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7e is H or an organic group. 7e may be the same or different. In formula (e), Ae Ha-COOM e This is one of the preferred embodiments.

[0798] R 7e The organic group in R is preferably an alkyl group. 7e 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.

[0799] M e The group may be H, a metal atom, or NR 7e 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7e 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.

[0800] In formula (e), Y e are the same or different in each occurrence, and are -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8e - and -NR 8e a divalent linking group selected from the group consisting of CO—, or a bond, R 8e represents H or an organic group.

[0801] Y e Examples include bonds, -O-, -COO-, -OCO-, and -CONR. 8e - and -NR 8e 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.

[0802] R 8e The organic group in R is preferably an alkyl group. 8e As for H or C 1-10is 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.

[0803] In formula (e), R 6e 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. 6e The organic group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.

[0804] R 6e 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. 6e In the alkyl 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 alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0805] R 6e As for General formula:-R 10e -CO-R 11e a group represented by General formula:-R 10e -COO-R 11e a group represented by General formula:-R 11e a group represented by General formula:-R 10e -NR 8e CO-R 11e or a group represented by General formula:-R 10e -CONR 8e -R 11e a group represented by (In the formula, R 8e represents H or an organic group.10e is an alkylene group, R 11e is preferably an alkyl group which may have a substituent. R 6e As the general formula: -R 10e -CO-R 11e A group represented by the following formula is more preferred.

[0806] R 8e The organic group in R is preferably an alkyl group. 8e 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.

[0807] R 10e 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. 10e 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.

[0808] R 11e 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. 11e 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. 11e 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.

[0809] In formula (e), R 2e and R 5e At least one of the groups has the general formula: -X e -A e and A is a group represented by the formula: eHa-COOM e In one preferred embodiment,

[0810] As the surfactant (e), a compound represented by general formula (e-1), a compound represented by general formula (e-2), or a compound represented by general formula (e-3) is preferred, and a compound represented by general formula (e-1) or a compound represented by general formula (e-2) is more preferred.

[0811] General formula (e-1): [ka] (In the formula, R 3e ~R 6e , X e , A e and Y e is as above.)

[0812] General formula (e-2): [ka] (In the formula, R 4e ~R 6e , X e , A e and Y e is as above.)

[0813] General formula (e-3): [ka] (In the formula, R 2e , R 4e ~R 6e , X e , A e and Y e is as above.)

[0814] General formula:-X e -A e Examples of the group represented by the formula: -COOM e , -R 12e COOM e , -SO3Me , -OSO3M e , -R 12e SO3M e , -R 12e OSO3M e , -OCO-R 12e -COOM e , -OCO-R 12e -SO3M e , -OCO-R 12e -OSO3M e , -COO-R 12e -COOM e , -COO-R 12e -SO3M e , -COO-R 12e -OSO3M e , -CONR 8e -R 12e -COOM e , -CONR 8e -R 12e -SO3M e , -CONR 8e -R 12e -OSO3M e , -NR 8e CO-R 12e -COOM e , -NR 8e CO-R 12e -SO3M e , -NR 8e CO-R 12e -OSO3M e , -OS(=O)2-R 12e -COOM e , -OS(=O)2-R 12e -SO3M e , or -OS(=O)2-R 12e -OSO3Me (In the formula, R 8e and M e As mentioned above, R 12e is C 1-10 An alkylene group represented by the formula: is preferred. Above R 12e 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.

[0815] General formula:-Y e -R 6e Examples of the group represented by the formula: General formula:-R 10e -CO-R 11e a group represented by General formula:-OCO-R 10e -CO-R 11e a group represented by General formula:-COO-R 10e -CO-R 11e a group represented by General formula:-OCO-R 10e -COO-R 11e a group represented by General formula:-COO-R 11e a group represented by the group represented by General formula:-NR 8e CO-R 10e -CO-R 11e or a group represented by General formula:-CONR 8e -R 10e -NR 8e CO-R 11e A group represented by (In the formula, R 8e , R 10e and R 11e is as described above.) is preferred.

[0816] In the formula, R 4e and R 5e are independently H or C1-4 The alkyl groups are preferably: Above R 4e and R 5e In the alkyl 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 alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0817] R in general formula (e-1) 3e 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 3e In the alkyl 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 alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0818] R in general formula (e-3) 2e 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 2e In the alkyl 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 alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0819] The surfactant (e) can be produced by a known production method.

[0820] The specific hydrocarbon surfactant is preferably a carboxylic acid type hydrocarbon surfactant. The carboxylic acid type hydrocarbon surfactant 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 specific 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.

[0821] The carboxylic acid type hydrocarbon surfactant is preferably at least one selected from the group consisting of surfactants (c) represented by the above formula (c) and surfactants (d) represented by the above formula (d), which have 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.).

[0822] The PTFE of the present disclosure can be efficiently produced by using at least one of the above-mentioned specific hydrocarbon surfactants. The PTFE of the present disclosure may also be produced by simultaneously using two or more of the above-mentioned specific hydrocarbon surfactants, or by simultaneously using a compound having surface activity other than the above-mentioned specific hydrocarbon surfactants, as long as it is volatile or may remain in a molded product made of PTFE, etc.

[0823] As the other compounds having surface activity, for example, those described in JP-A Nos. 2013-542308, 2013-542309, and 2013-542310 can be used.

[0824] Other surface-active compounds may be surfactants having a hydrophilic portion and a hydrophobic portion on the same molecule, such as hydrocarbon surfactants, which may be cationic, nonionic, or anionic.

[0825] Cationic 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.

[0826] Anionic 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.

[0827] Nonionic 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 water-soluble functional groups, such as ethylene ether chains derived from polymerization with ethylene oxide.

[0828] Examples of nonionic surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

[0829] Specific examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene behenyl ether.

[0830] Specific examples of polyoxyethylene alkylphenyl ethers include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0831] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.

[0832] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0833] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0834] Specific examples of glycerol esters include glycerol monomyristate, glycerol monostearate, and glycerol monooleate.

[0835] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

[0836] The ethers and esters may have an HLB value of 10-18.

[0837] Examples of nonionic surfactants include Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), and Tergitol (registered trademark) L series, all manufactured by Dow Chemical Company; Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m to 22, n to 23)) and Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10), all manufactured by BASF.

[0838] 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.

[0839] Other compounds having surface activity include RLM (wherein R is a linear or branched alkyl group having one or more carbon atoms which may have a substituent, or a cyclic alkyl 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). L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M is H, a metal atom, or NR 5 4(R 5 may be the same or different and are H or an organic group), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate. ) 5 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. 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). Mixtures in which R 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 6 (-LM)2(wherein, R 6 is a linear or branched alkylene group having one or more carbon atoms which may have a substituent, or a cyclic alkylene 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 54. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 5 is H or an organic group, -ArSO3 - is an aryl sulfonate. ) Other surfactant compounds include R 7 (-LM)3(wherein, R 7 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 5 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 5 is H or an organic group. -ArSO3 - is an aryl sulfonate. )

[0840] Siloxane hydrocarbon surfactants include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of the siloxane surfactant comprises a distinct hydrophobic portion and a hydrophilic portion. The hydrophobic portion comprises one or more dihydrocarbylsiloxane units, where the substituents on the silicone atom are entirely hydrocarbon. These siloxane surfactants can also be considered hydrocarbon surfactants in the sense that the carbon atoms of the hydrocarbyl groups are fully substituted by hydrogen atoms, which may be substituted by halogens such as fluorine, i.e., the monovalent substituents on the carbon atoms of the hydrocarbyl groups are hydrogen.

[0841] 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 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.

[0842] 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 hydrocarbon surfactants.

[0843] 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 hydrocarbon surfactant may comprise a graft polymer.

[0844] Siloxane hydrocarbon surfactants are also disclosed in US Pat. No. 6,841,616.

[0845] Siloxane-based anionic hydrocarbon surfactants include SilSense available from Noveon® Consumer Specialties, manufactured by Lubrizol Advanced Materials, Inc. TM PE-100 Silicone, SilSense TM CA-1 silicone and the like.

[0846] Examples of anionic hydrocarbon surfactants include the sulfosuccinate surfactant Lankropol (registered trademark) K8300 manufactured by Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate surfactants include sodium diisodecyl sulfosuccinate (Emulsogen (registered trademark) SB10 manufactured by Clariant) and sodium diisotridecyl sulfosuccinate (Polirol (registered trademark) TR / LNA manufactured by Cesapinia Chemicals).

[0847] Other surfactant compounds include PolyFox (registered trademark) surfactants manufactured by Omnova Solutions, Inc. TM PF-156A, PolyFox TM PF-136A, etc.)

[0848] The other surfactant compound is preferably an anionic hydrocarbon surfactant. As the anionic hydrocarbon surfactant, those described above can be used, but for example, the following hydrocarbon surfactants can be suitably used.

[0849] Examples of the anionic hydrocarbon surfactant include those represented by the following formula (α): R 100 -COOM (α) (In the formula, R 100 is a monovalent organic group containing one or more carbon atoms. M is H, a metal atom, NR 101 4. An 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 is preferably Na, K, or Li. M may be 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.

[0850] 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 number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above.) Specifically, CH3-(CH2) n-COOM (wherein n is an integer of 2 to 28, and M is the same as above).

[0851] 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 (B): R 103 -COO-M (B) (In the formu...

Claims

1. Tetrafluoroethylene homopolymer, or tetrafluoroethylene and modified monomer (CH ２ =CR １ -L-R ２ (R １ represents a hydrogen atom or an alkyl group. L represents a single bond, -CO-O-*, -O-CO-* or -O-. * represents R ２ represents the bonding position with ２ represents a hydrogen atom, an alkyl group, or a nitrile group.) is excluded. A method for producing polytetrafluoroethylene which is a copolymer with a monomer represented by the formula (I) and has a content of modified monomer units of 0.00001 to 1.0 mass %, comprising the steps of: The breaking strength of the polytetrafluoroethylene is 16.2 N or more and 36.0 N or less, The thermal instability index (TII) of the polytetrafluoroethylene is 34 or more and 50 or less, a polymerization step of carrying out emulsion polymerization of only the tetrafluoroethylene or emulsion polymerization of the tetrafluoroethylene and the modifying monomer in an aqueous medium in the presence of a hydrocarbon surfactant, The hydrocarbon surfactant is A hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) that has been subjected to radical treatment or oxidation treatment, or A compound (α) represented by the following formula (α), a surfactant (1-0A) represented by the following formula (1-0A), the compound (α) subjected to a radical treatment or an oxidation treatment, or the surfactant (1-0A) subjected to a radical treatment or an oxidation treatment, The compound (α) and the compound (α) subjected to radical treatment or oxidation treatment include, at least in part, those in which the following M is 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: The surfactant (1-0A) and the surfactant (1-0A) subjected to radical treatment or oxidation treatment include, at least in part, those in which the following M is 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: In the polymerization step, the hydrocarbon surfactant is continuously added. A method for producing polytetrafluoroethylene, comprising the steps of: R 100 -COOM (α) (In formula (α), R 100 is a monovalent organic group containing one or more carbon atoms. 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, and R 101 is H or an organic group, which may be the same or different.) 【Chemistry 123】 (In formula (1-0A), R 1A to R 5A are H, a monovalent hydrocarbon group which may contain an ester group between the carbon-carbon atoms, or a group represented by the general formula -X A -A, provided that at least one of R 2A and R 5A represents a group represented by the general formula -X A -A. X A is the same or different in each occurrence and is a divalent hydrocarbon group 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, and R 7 is H or an organic group); any two of R 1A to R 5A may be bonded to each other to form a ring.)

2. Tetrafluoroethylene homopolymer, or tetrafluoroethylene and modified monomer (CH ２ =CR １ -L-R ２ (R １ represents a hydrogen atom or an alkyl group. L represents a single bond, -CO-O-*, -O-CO-* or -O-. * represents R ２ represents the bonding position with ２ represents a hydrogen atom, an alkyl group, or a nitrile group.) is excluded. A method for producing polytetrafluoroethylene which is a copolymer with a monomer represented by the formula (I) and has a content of modified monomer units of 0.00001 to 1.0 mass %, comprising the steps of: The standard specific gravity of the polytetrafluoroethylene is 2.151 or more and 2.175 or less, The polytetrafluoroethylene has a 0.1% mass loss temperature of 364° C. or higher and 397° C. or lower; a polymerization step of carrying out emulsion polymerization of only the tetrafluoroethylene or emulsion polymerization of the tetrafluoroethylene and the modifying monomer in an aqueous medium in the presence of a hydrocarbon surfactant, The hydrocarbon surfactant is A hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) that has been subjected to radical treatment or oxidation treatment, or A compound (α) represented by the following formula (α), a surfactant (1-0A) represented by the following formula (1-0A), the compound (α) subjected to a radical treatment or an oxidation treatment, or the surfactant (1-0A) subjected to a radical treatment or an oxidation treatment, The compound (α) and the compound (α) subjected to radical treatment or oxidation treatment include, at least in part, those in which the following M is 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: The surfactant (1-0A) and the surfactant (1-0A) subjected to radical treatment or oxidation treatment include, at least in part, those in which the following M is 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: In the polymerization step, the hydrocarbon surfactant is continuously added. A method for producing polytetrafluoroethylene, comprising the steps of: R 100 -COOM (α) (In formula (α), R 100 is a monovalent organic group containing one or more carbon atoms. 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, and R 101 is H or an organic group, which may be the same or different.) 【Chemistry 124】 (In formula (1-0A), R 1A to R 5A are H, a monovalent hydrocarbon group which may contain an ester group between the carbon-carbon atoms, or a group represented by the general formula -X A -A, provided that at least one of R 2A and R 5A represents a group represented by the general formula -X A -A. X A is the same or different in each occurrence and is a divalent hydrocarbon group 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, and R 7 is H or an organic group); any two of R 1A to R 5A may be bonded to each other to form a ring.)

3. Tetrafluoroethylene homopolymer, or tetrafluoroethylene and modified monomer (CH ２ =CR １ -L-R ２ (R １ represents a hydrogen atom or an alkyl group. L represents a single bond, -CO-O-*, -O-CO-* or -O-. * represents R ２ represents the bonding position with ２ represents a hydrogen atom, an alkyl group, or a nitrile group.) is excluded. A method for producing polytetrafluoroethylene which is a copolymer with a monomer represented by the formula (I) and has a content of modified monomer units of 0.00001 to 1.0 mass %, comprising the steps of: The standard specific gravity of the polytetrafluoroethylene is 2.151 or more and 2.175 or less, The polytetrafluoroethylene has a 0.1% mass loss temperature of 364° C. or higher and a 1.0% mass loss temperature of 492° C. or lower; a polymerization step of carrying out emulsion polymerization of only the tetrafluoroethylene or emulsion polymerization of the tetrafluoroethylene and the modifying monomer in an aqueous medium in the presence of a hydrocarbon surfactant, The hydrocarbon surfactant is A hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups), or a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) that has been subjected to radical treatment or oxidation treatment, or A compound (α) represented by the following formula (α), a surfactant (1-0A) represented by the following formula (1-0A), the compound (α) subjected to a radical treatment or an oxidation treatment, or the surfactant (1-0A) subjected to a radical treatment or an oxidation treatment, The compound (α) and the compound (α) subjected to radical treatment or oxidation treatment include, at least in part, those in which the following M is 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: The surfactant (1-0A) and the surfactant (1-0A) subjected to radical treatment or oxidation treatment include, at least in part, those in which the following M is 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: In the polymerization step, the hydrocarbon surfactant is continuously added. A method for producing polytetrafluoroethylene, comprising the steps of: R 100 -COOM (α) (In formula (α), R 100 is a monovalent organic group containing one or more carbon atoms. 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, and R 101 is H or an organic group, which may be the same or different.) 【Chemistry 125】 (In formula (1-0A), R 1A to R 5A are H, a monovalent hydrocarbon group which may contain an ester group between the carbon-carbon atoms, or a group represented by the general formula -X A -A, provided that at least one of R 2A and R 5A represents a group represented by the general formula -X A -A. X A is the same or different in each occurrence and is a divalent hydrocarbon group 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, and R 7 is H or an organic group); any two of R 1A to R 5A may be bonded to each other to form a ring.)

4. The polytetrafluoroethylene has a stress relaxation time of 50 seconds or more and 312 seconds or less. The method for producing polytetrafluoroethylene according to any one of claims 1 to 3.

5. The extrusion pressure of the polytetrafluoroethylene is 8.0 MPa or more and 30.0 MPa or less. The method for producing polytetrafluoroethylene according to any one of claims 1 to 4.

6. The polytetrafluoroethylene is molded and heat-treated at 100° C. for 2 hours, at 200° C. for 4 hours, and at 370° C. for 5 hours, and a sheet cut from the sintered body has a lightness L* of 46 or more and 90.0 or less. The method for producing polytetrafluoroethylene according to any one of claims 1 to 5.

7. The polytetrafluoroethylene is molded and heat-treated at 100° C. for 2 hours, at 200° C. for 4 hours, and at 370° C. for 5 hours to obtain a fired body having a thermal shrinkage rate of 7.0% or more and 7.4% or less. The method for producing polytetrafluoroethylene according to any one of claims 1 to 6.

8. The polytetrafluoroethylene is molded and heat-treated at 100° C. for 2 hours, at 200° C. for 4 hours, and at 370° C. for 5 hours to obtain a fired body. A sheet is cut from the fired body, and the contact angle of the surface of the fired body corresponding to the inside of the fired body is 107° or more and 114° or less. The method for producing polytetrafluoroethylene according to any one of claims 1 to 7.

9. The method for producing polytetrafluoroethylene according to any one of claims 1 to 8, wherein the polytetrafluoroethylene is in the form of a powder.

10. A method for producing an extruded body, comprising the steps of obtaining polytetrafluoroethylene by the method according to any one of claims 1 to 9 and extruding the polytetrafluoroethylene.

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