Method for producing purified polytetrafluoroethylene aqueous dispersion liquid, method for producing modified polytetrafluoroethylene powder, method for producing polytetrafluoroethylene molded body, and composition

Abstract

To provide a polytetrafluoroethylene aqueous dispersion liquid from which fluorine-containing compounds have been removed or reduced.SOLUTION: The present invention discloses a method for producing a purified polytetrafluoroethylene aqueous dispersion liquid, the method including a step of removing or reducing compounds represented by general formula (1) or (2) from a polytetrafluoroethylene aqueous dispersion liquid prepared with a hydrocarbon-based surfactant. General formula (1): (H-(CF2)m-COO)pM1. General formula (2): (H-(CF2)n-SO3)qM2.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a purified polytetrafluoroethylene aqueous dispersion, a method for producing a modified polytetrafluoroethylene powder, and a method for producing a polytetrafluoroethylene molded article. [Background technology]

[0002] Conventionally, a method for producing polytetrafluoroethylene using a hydrocarbon surfactant has been known (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2013-542309 Summary of the Invention [Problem to be solved by the invention]

[0004] It has been discovered that the production of polytetrafluoroethylene using a hydrocarbon surfactant results in the production of certain fluorine-containing compounds. An object of the present invention is to obtain an aqueous polytetrafluoroethylene dispersion and polytetrafluoroethylene powder from which the above-mentioned fluorine-containing compounds have been removed or reduced. Another object of the present invention is to produce a polytetrafluoroethylene molded article from which the above-mentioned fluorine-containing compounds have been removed or reduced, using polytetrafluoroethylene obtained using a hydrocarbon surfactant. A further object of the present invention is to provide a composition containing polytetrafluoroethylene from which the above-mentioned fluorine-containing compounds have been removed or reduced. [Means for solving the problem]

[0005] The present invention is a method for producing a purified aqueous polytetrafluoroethylene dispersion, which comprises a step of removing or reducing the amount of a compound represented by the following general formula (1) or (2) from an aqueous polytetrafluoroethylene dispersion obtained using a hydrocarbon surfactant: General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The step of removing or reducing the compound represented by the general formula (1) or (2) above preferably includes a step of subjecting the aqueous polytetrafluoroethylene dispersion to an ion exchange treatment and / or a concentration treatment.

[0006] The present invention also provides a method for producing a modified polytetrafluoroethylene powder, which comprises a step of removing or reducing the amount of a compound represented by the following general formula (1) or (2) from a polytetrafluoroethylene powder obtained using a hydrocarbon surfactant: General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The step of removing or reducing the compound represented by the general formula (1) or (2) above preferably includes a step of heat-treating the polytetrafluoroethylene powder obtained using a hydrocarbon surfactant at a temperature of 160°C or higher.

[0007] The present invention further provides a method for producing a molded article using polytetrafluoroethylene produced using a hydrocarbon surfactant, the method comprising the step of removing or reducing a compound represented by the following general formula (1) or (2): General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The step of removing or reducing the compound represented by the general formula (1) or (2) preferably includes a step of heat treatment at a temperature of 160° C. or higher.

[0008] The present invention also relates to a method for producing modified polytetrafluoroethylene, which comprises the step of contacting polytetrafluoroethylene obtained using a hydrocarbon surfactant with a fluorine radical source at a temperature above 100°C to remove or reduce the amount of a compound represented by the following general formula (1) or (2): General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.

[0009] The present invention also relates to a method for producing polytetrafluoroethylene, comprising the step of contacting polytetrafluoroethylene obtained using a hydrocarbon surfactant with a fluorine radical source to remove or reduce the amount of a compound represented by the following general formula (1) or (2), wherein the amount of the fluorine radical source added is 0.5 parts by weight or more, calculated as fluorine atoms, per 100 parts by weight of polytetrafluoroethylene: General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2.

[0010] The present invention also provides a composition containing polytetrafluoroethylene and substantially free of a compound represented by the following general formula (3): General formula (3): (H-(CF2)8-SO3) q M 2 (In the formula, M 2 is H, metal atom, NR 5 4(R 5may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The content of the compound represented by the general formula (3) is preferably 1000 ppb or less, more preferably 25 ppb or less, based on polytetrafluoroethylene.

[0011] One aspect of the present invention is a composition containing a compound represented by the following general formula (4) at 1000 ppb or less relative to polytetrafluoroethylene, and a nonionic surfactant at 1% / polytetrafluoroethylene or more. General formula (4): (H-(CF2)7-COO) p M 1 (In the formula, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. One aspect of the present invention is a composition containing at least one of a compound represented by the above general formula (4) and a compound represented by the following general formula (4'), wherein the content of the compound represented by the above general formula (4) is 1000 ppb or less relative to polytetrafluoroethylene, the content of the compound represented by the following general formula (4') is 1000 ppb or less relative to polytetrafluoroethylene, and ... composition contains a nonionic surfactant at 1% / polytetrafluoroethylene or more. General formula (4'):(H-(CF2)8-COO) p M 1 (In the formula, M 1 is H, metal atom, NR 5 4(R 5may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. One aspect of the present invention is a composition containing a compound represented by the following general formula (5) at 1000 ppb or less relative to polytetrafluoroethylene, and a nonionic surfactant at 1% / polytetrafluoroethylene or more. General formula (5):(H-(CF2) 13 -COO) p M 1 (In the formula, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. One aspect of the present invention is a composition containing at least one of a compound represented by the above general formula (5) and a compound represented by the following general formula (5'), wherein the content of the compound represented by the above general formula (5) is 1000 ppb or less relative to polytetrafluoroethylene, the content of the compound represented by the following general formula (5') is 1000 ppb or less relative to polytetrafluoroethylene, and ... composition contains a nonionic surfactant in an amount of 1% / polytetrafluoroethylene or more. General formula (5'):(H-(CF2) 14 -COO) p M 1 (In the formula, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. One aspect of these inventions is a composition that is an aqueous dispersion.

[0012] One aspect of the present invention is a composition containing a compound represented by the general formula (4) at a concentration of 1000 ppb or less relative to polytetrafluoroethylene. The present invention is also a composition containing at least one of a compound represented by the general formula (4) and a compound represented by the general formula (4'), wherein the content of the compound represented by the general formula (4) is 1000 ppb or less relative to polytetrafluoroethylene, and the content of the compound represented by the general formula (4') is 1000 ppb or less relative to polytetrafluoroethylene. The present invention is also a composition containing a compound represented by the general formula (5) at a concentration of 1000 ppb or less relative to polytetrafluoroethylene. Another aspect of the present invention is a composition containing at least one of a compound represented by the general formula (5) and a compound represented by the general formula (5'), wherein the content of the compound represented by the general formula (5) is 1000 ppb or less relative to polytetrafluoroethylene, and the content of the compound represented by the general formula (5') is 1000 ppb or less relative to polytetrafluoroethylene. Another aspect of the present invention is a composition containing a compound represented by the general formula (4) at a concentration of 25 ppb or less relative to polytetrafluoroethylene. Another aspect of the present invention is a composition containing at least one of a compound represented by the general formula (4) and a compound represented by the general formula (4'), wherein the content of the compound represented by the general formula (4) is 25 ppb or less relative to polytetrafluoroethylene, and the content of the compound represented by the general formula (4') is 25 ppb or less relative to polytetrafluoroethylene. Another aspect of the present invention is a composition containing a compound represented by the general formula (5) at a concentration of 25 ppb or less relative to polytetrafluoroethylene. Another aspect of the present invention is a composition containing at least one of a compound represented by the general formula (5) and a compound represented by the general formula (5'), wherein the content of the compound represented by the general formula (5) is 25 ppb or less relative to polytetrafluoroethylene, and the content of the compound represented by the general formula (5') is 25 ppb or less relative to polytetrafluoroethylene. The composition may further contain a compound represented by the following general formula (7) in an amount of 1000 ppb or less relative to polytetrafluoroethylene. General formula (7): (F-(CF2)7-COO) p M 1 (In the formula, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. One aspect of these inventions is a composition that is a powder.

[0013] The composition of the present invention is preferably one obtained by polymerizing polytetrafluoroethylene using a hydrocarbon surfactant.

[0014] The present invention also relates to a molded article made of the above composition. The molded article of the present invention is also preferably a stretched article. [Effects of the Invention]

[0015] The method for producing a purified aqueous polytetrafluoroethylene dispersion of the present invention can remove or reduce the amount of the compound represented by general formula (1) or (2) present in the resulting purified aqueous PTFE dispersion. The method for producing modified polytetrafluoroethylene powder of the present invention can remove or reduce the amount of the compound represented by general formula (1) or (2) present in the obtained modified polytetrafluoroethylene powder. The method for producing a polytetrafluoroethylene molded article of the present invention can remove or reduce the amount of the compound represented by general formula (1) or (2) present in the obtained polytetrafluoroethylene molded article. The composition of the present invention is one in which the compound represented by general formula (3) is removed or reduced. DETAILED DESCRIPTION OF THE INVENTION

[0016] The method for producing a purified aqueous PTFE dispersion of the present invention includes a step of removing or reducing the amount of the compound represented by general formula (1) or (2) from an aqueous dispersion of polytetrafluoroethylene (hereinafter, sometimes referred to as "PTFE") obtained using a hydrocarbon surfactant (hereinafter, also referred to as the "removal step"). General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (Group 1) or alkaline earth metal (Group 2), and specific examples include Na, K, and Li. Above R 5 The four R's 5 may be the same or different. 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. It is also preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. All of the R 5 The above provisions are applicable to: In the general formula (1), m may be 5 to 11. In the general formula (2), n may be 6 to 12.

[0017] In this specification, unless otherwise specified, the term "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. Examples of the "organic group" are: an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents; cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, and RaOSO2- (In these formulas, Ra independently represents: an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents Includes. The organic group is preferably an alkyl group which may have one or more substituents. The organic group also includes those listed above as examples of the substituent. In this specification, unless otherwise specified, the term "substituent" refers to a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an and hydroxy groups, cyano groups, sulfo groups, carboxy groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, and diaromatic oxyphosphinyl groups.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] The aliphatic thio group may be saturated or unsaturated and is an alkylthio group 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, or a t-butylthio group.

[0034] 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.

[0035] The PTFE may be either homo-PTFE or modified PTFE. The modified PTFE contains TFE units and modified monomer units based on a modified monomer copolymerizable with TFE. The PTFE may be a high molecular weight PTFE that is non-melt processable and has fibrillating properties, or a low molecular weight PTFE that is melt processable but does not have fibrillating properties. The standard specific gravity (SSG) and melt viscosity (MV) used as indicators of the molecular weight of PTFE are not particularly limited.

[0036] The modifying monomer is not particularly limited as long as it is copolymerizable with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene (HFP), chlorofluoroolefins such as chlorotrifluoroethylene (CTFE), hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF), perfluorovinyl ethers, perfluoroalkylethylenes, ethylene, fluorine-containing vinyl ethers having a nitrile group, etc. The modifying monomer used may be one type or multiple types.

[0037] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (X): CF2=CF-ORf (X) (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.

[0038] An example of the perfluorovinyl ether is perfluoro(alkyl vinyl ether) [PAVE], where Rf in the general formula (X) represents a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0039] Examples of the perfluoroalkyl group in the PAVE include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl groups. Preferred are purple methyl vinyl ether (PMVE), in which the perfluoroalkyl group is a perfluoromethyl group, and purple propyl vinyl ether (PPVE), in which the perfluoroalkyl group is a perfluoropropyl group.

[0040] The perfluoroalkylethylene is not particularly limited, and examples thereof include perfluorobutylethylene (PFBE), perfluorohexylethylene (PFHE), and perfluorooctylethylene (PFOE).

[0041] The modifying monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PMVE, PPVE, PFBE, PFHE, CNVE and ethylene.

[0042] The modified PTFE preferably contains modified monomer units in the range of 0.0001 to 2 mol %, more preferably 0.0001 to less than 1 mol %, even more preferably 0.0001 to 0.5 mol %, and particularly preferably 0.001 to 0.2 mol %.

[0043] The average primary particle diameter of the PTFE is preferably 150 nm or more, more preferably 180 nm or more. The larger the average primary particle diameter of the PTFE composition, 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, it 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 obtained 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.

[0044] The PTFE may have a core-shell structure. Examples of PTFE having a core-shell structure include modified PTFE particles containing a core of high molecular weight PTFE and a shell of lower molecular weight PTFE or modified PTFE. An example of such modified PTFE is the PTFE described in JP-A-2005-527652.

[0045] 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.

[0046] The method for obtaining an aqueous PTFE dispersion using a hydrocarbon surfactant will be described later. The aqueous PTFE dispersion obtained using a hydrocarbon surfactant contains the compound represented by the above general formula (1) or (2).

[0047] Methods for removing or reducing the amount of the compound represented by general formula (1) or (2) from the aqueous PTFE dispersion include adsorption treatment, concentration treatment, and the like. Alternatively, a method can be employed in which the aqueous PTFE dispersion is dried and evaporated to remove or reduce the amount of the compound represented by general formula (1) or (2). As the drying temperature, for example, the temperature of the heat treatment described below can be used. Furthermore, a method may be mentioned in which an aqueous PTFE dispersion is gasified, and the compound represented by general formula (1) or (2) in the gas is absorbed into an aqueous liquid using a droplet type absorber and / or a liquid film type absorber. The temperature of the aqueous liquid is preferably, for example, 10 to 60°C.

[0048] Examples of the adsorption treatment include methods using adsorbents such as ion exchange resin (IER), activated carbon, and zeolite. Specifically, the compound represented by general formula (1) or (2) contained in the PTFE aqueous dispersion can be removed or reduced by contacting the compound with an adsorbent. The adsorption treatment can be carried out by adding an ion exchange resin to the PTFE aqueous dispersion and stirring as necessary. The ion exchange treatment is preferably carried out by adding 1 g or more of ion exchange resin per 100 g of PTFE. The amount of ion exchange resin added is more preferably 10 g or more, and is preferably 200 g or less, more preferably 100 g or less.

[0049] Examples of the concentration treatment include phase separation concentration, electrical concentration, filtration using an ultrafiltration membrane, filtration using a reverse osmosis membrane (RO membrane), nanofiltration, etc. Examples of the concentration treatment include a method in which a nonionic surfactant is added to an aqueous PTFE dispersion to a concentration of 1% / PTFE or more, and the dispersion is allowed to stand. The amount of nonionic surfactant added is preferably 40% / PTFE or less, more preferably 30% / PTFE or less, and even more preferably 20% / PTFE or less. The temperature at which the mixture is left standing is not limited, but may be, for example, 20° C. or higher and 80° C. or lower. The time period for which the mixture is left standing is not limited, but may be, for example, 1 minute or longer and 24 hours or shorter.

[0050] The removing step preferably includes a step of subjecting the aqueous PTFE dispersion to an adsorption treatment and / or a concentration treatment, and more preferably includes a step of subjecting the aqueous PTFE dispersion to an ion exchange treatment and / or a concentration treatment. The step of performing ion exchange treatment and / or concentration treatment may be a step of performing ion exchange treatment, a step of performing concentration treatment, or a step of performing ion exchange treatment and concentration treatment, and each treatment may be performed multiple times. When performing ion exchange treatment and concentration treatment, the order of the ion exchange treatment and the concentration treatment may be random, or may be performed alternately. The ion exchange treatment and / or concentration treatment step is particularly preferably a step of performing an ion exchange treatment and a concentration treatment. The ion exchange treatment and / or concentration treatment step is more preferably a step of performing an ion exchange treatment followed by a concentration treatment.

[0051] The adsorption treatment and concentration treatment may each be performed multiple times. For example, the adsorption treatment or concentration treatment may be performed 2, 3, 4, 5, 6, 7, 8, 9, or 10 times. The adsorption treatment and concentration treatment may also be performed in combination.

[0052] When a PTFE aqueous dispersion is obtained using a hydrocarbon surfactant, the compounds represented by the general formulas (1) and (2) are usually produced in an amount of 1 to 200 ppm relative to the PTFE. By the above-mentioned removal step, the compound represented by the general formula (1) or (2) in the aqueous PTFE dispersion is removed or reduced, and a purified aqueous PTFE dispersion can be obtained.

[0053] The removal step preferably removes 80% by mass or more of the compounds represented by general formulas (1) and (2) in the PTFE aqueous dispersion, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, especially preferably 97% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass or more.

[0054] The removal step is carried out so that the content of the compounds represented by general formulas (1) and (2) in the resulting purified PTFE aqueous dispersion is reduced to preferably 500 ppb or less, more preferably 200 ppb or less, even more preferably 100 ppb or less, particularly preferably 50 ppb or less, and most preferably 25 ppb or less, relative to PTFE.

[0055] The PTFE aqueous dispersion can be obtained by a production method including a step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon surfactant. The emulsion polymerization can be carried out by a conventionally known method. The aqueous medium is not particularly limited as long as it is a liquid containing water, and may contain, in addition to water, an organic solvent such as alcohol, ether, ketone, or paraffin wax.

[0056] Examples of the hydrocarbon surfactant that can be used include those described in JP-A Nos. 2013-542308, 2013-542309, and 2013-542310. Details of the hydrocarbon surfactant will be described later.

[0057] The present invention also provides a method for producing a modified PTFE powder, which comprises a step of removing the compound represented by the following general formula (1) or (2) from the PTFE powder obtained using a hydrocarbon surfactant: General formula (1):(H-(CF2) m -COO) p M 1(wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (Group 1) or alkaline earth metal (Group 2), and specific examples include Na, K, and Li. Above R 5 The four R's 5 may be the same or different. 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. In the general formula (1), m may be 5 to 11. In the general formula (2), n may be 6 to 12.

[0058] The PTFE powder obtained using a hydrocarbon surfactant can be obtained, for example, by coagulating the aqueous PTFE dispersion obtained using the above-mentioned hydrocarbon surfactant. As the PTFE in the PTFE powder, PTFE such as homo-PTFE or modified PTFE described in the method for producing the purified aqueous PTFE dispersion can be used.

[0059] Methods for removing or reducing the amount of the compound represented by general formula (1) or (2) from the PTFE powder include heat treatment, fluorination treatment, washing with water or an organic solvent, and the like. Examples of the organic solvent include ethers, halogenated hydrocarbons, aromatic hydrocarbons, pyridine, nitriles, nitrogen-containing polar organic compounds, dimethyl sulfoxide, and alcohols. Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether. Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene. Examples of the aromatic hydrocarbon include benzene, toluene, and xylene. Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile. 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. Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol. The above organic solvents may be used in combination.

[0060] The heat treatment method is not particularly limited, and any conventionally known method can be used. The heat treatment temperature is preferably 150°C or higher. From the viewpoint of removing or reducing the compound represented by general formula (1) or (2), the heat treatment temperature is more preferably 160°C or higher. That is, the removal step preferably includes a step of heat treating the PTFE powder obtained using the hydrocarbon surfactant at a temperature of 160°C or higher. The temperature of the heat treatment is more preferably 170°C or higher, even more preferably 180°C or higher, even more preferably 200°C or higher, particularly preferably 210°C or higher, particularly preferably 220°C or higher, and most preferably 230°C or higher. The temperature of the heat treatment is preferably 310° C. or less, more preferably 300° C. or less, even more preferably 290° C. or less, even more preferably 280° C. or less, and particularly preferably 270° C. or less. The heat treatment may be accompanied by drying of moisture. That is, the heat treatment may be a process of drying a wet PTFE powder containing water obtained by coagulating a PTFE dispersion obtained after polymerization using a hydrocarbon surfactant. During drying, the compounds represented by general formula (1) or (2) and the compounds represented by general formula (7) described below are reduced. It is also preferable to heat-treat the PTFE powder free from moisture after drying again. Specifically, the wet PTFE powder may be dried to remove moisture, and then the temperature may be continuously increased to the above-mentioned temperature range to perform heat treatment. In this case, the drying may be performed at a temperature lower than the above-mentioned temperature ranges, for example, lower than 150°C. The method for producing the modified PTFE powder of the present invention may include a step of coagulating the obtained PTFE dispersion using a hydrocarbon surfactant to obtain a wet PTFE powder containing water.

[0061] As the fluorination treatment method, a conventionally known method can be used. For example, a method of exposing the PTFE powder to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions can be used. In addition to fluorine gas, the fluorine radical source can also be CoF3, AgF2, UF6, OF2, N2F2, CF3OF, halogen fluorides (e.g., IF, IF3, IF5, IF7, etc.), etc. n (n is 1 to 7; ClF, ClF3, BrF3, etc.), rare gas fluorides (XeF2, XeF4, KrF2, etc.), and nitrogen-containing fluorine compounds (NF3, NF2, etc.). Among these, fluorine gas is most preferred from the viewpoints of ease of handling and cost, ability to remove compounds represented by general formulas (1) and (2) with high efficiency, and the fact that it is unlikely to give rise to new impurities such as iodine. Since the reaction with the fluorine radical source is highly exothermic, the fluorine radical source may be diluted with an inert gas such as nitrogen. The level of fluorine radical source in the fluorine radical source / inert gas mixture can be from 1 to 100% by volume, but is preferably from about 5 to about 25% by volume due to the high hazards of working with pure fluorine. For fluoropolymer resins that exhibit severe thermally induced discoloration, the fluorine radical source / inert gas mixture may be sufficiently diluted to prevent overheating of the fluoropolymer and the attendant fire hazard.

[0062] The fluorination treatment method is not particularly limited, and conventionally known methods can be used. The fluorination treatment temperature is preferably above 100°C. The fluorination treatment temperature is more preferably 110°C or higher, even more preferably 120°C or higher, even more preferably 130°C or higher, and especially preferably 150°C or higher. It is particularly preferably 170°C or higher, even more preferably 180°C or higher, even more preferably 200°C or higher, especially preferably 210°C or higher, especially preferably 220°C or higher, and most preferably 230°C or higher. The fluorination treatment temperature is preferably 310°C or lower, more preferably 300°C or lower, even more preferably 290°C or lower, even more preferably 280°C or lower, especially preferably 270°C or lower, especially preferably 250°C or lower, and most preferably 240°C or lower. If the temperature is too low, the compound represented by the general formula (7) described below may remain at more than 1000 ppb relative to the PTFE. If the temperature is too high, friction between the PTFE powder particles can easily cause fibrillation even with a small shear force, leading to the loss of the original particle structure, which can result in a decrease in paste extrusion performance. The temperature for the fluorination treatment is preferably from 110 to 270°C, more preferably from 120 to 270°C, still more preferably from 150 to 270°C, and particularly preferably from 200 to 270°C.

[0063] In the above-mentioned fluorination treatment, the amount of the fluorine radical source added, calculated as fluorine atoms, is preferably 0.5 parts by weight or more per 100 parts by weight of the raw material PTFE. More preferably, it is 0.8 parts by weight or more, even more preferably 1.0 parts by weight or more, more preferably 1.6 parts by weight or more, even more preferably 2.0 parts by weight or more, even more preferably 2.5 parts by weight or more, especially preferably 3.0 parts by weight or more, and particularly preferably 5.0 parts by weight or more. Furthermore, the amount of the fluorine radical source added is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, even more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less. If the amount of the fluorine radical source added is too small, the removal or reduction of the compound represented by general formula (1) or (2) may be insufficient. Furthermore, the removal or reduction of unidentifiable compounds may be insufficient. If the amount of the fluorine radical source added is too large, the fluorination effect will not be improved and the process may be uneconomical.

[0064] A suitable combination of the fluorination treatment temperature and the amount of fluorine radical source added is a heat treatment temperature of over 100°C and an amount of the fluorine radical source added of 0.5 parts by weight or more, calculated as fluorine atoms, per 100 parts by weight of the raw material PTFE. The above combination is preferably above 100°C and 1.0 parts by weight or more, more preferably above 100°C and 1.6 parts by weight or more, even more preferably above 100°C and 2.0 parts by weight or more, even more preferably above 100°C and 2.5 parts by weight or more, especially preferably above 100°C and 3.0 parts by weight or more, and particularly preferably above 100°C and 5.0 parts by weight or more. Furthermore, 110°C or higher and 0.5 parts by weight or more are preferred, 110°C or higher and 1.0 parts by weight or more are more preferred, 110°C or higher and 1.6 parts by weight or more are even more preferred, 110°C or higher and 2.0 parts by weight or more are even more preferred, 110°C or higher and 2.5 parts by weight or more are particularly preferred, 110°C or higher and 3.0 parts by weight or more are particularly preferred, and 110°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 120°C or higher and 0.5 parts by weight or more are preferred, 120°C or higher and 1.0 parts by weight or more are more preferred, 120°C or higher and 1.6 parts by weight or more are even more preferred, 120°C or higher and 2.0 parts by weight or more are even more preferred, 120°C or higher and 2.5 parts by weight or more are particularly preferred, 120°C or higher and 3.0 parts by weight or more are particularly preferred, and 120°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 130°C or higher and 0.5 parts by weight or more are preferred, 130°C or higher and 1.0 parts by weight or more are more preferred, 130°C or higher and 1.6 parts by weight or more are even more preferred, 130°C or higher and 2.0 parts by weight or more are even more preferred, 130°C or higher and 2.5 parts by weight or more are particularly preferred, 130°C or higher and 3.0 parts by weight or more are particularly preferred, and 130°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 150°C or higher and 0.5 parts by weight or more are preferred, 150°C or higher and 1.0 parts by weight or more are more preferred, 150°C or higher and 1.6 parts by weight or more are even more preferred, 150°C or higher and 2.0 parts by weight or more are even more preferred, 150°C or higher and 2.5 parts by weight or more are particularly preferred, 150°C or higher and 3.0 parts by weight or more are particularly preferred, and 150°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 170°C or higher and 0.5 parts by weight or more are preferred, 170°C or higher and 1.0 parts by weight or more are more preferred, 170°C or higher and 1.6 parts by weight or more are even more preferred, 170°C or higher and 2.0 parts by weight or more are even more preferred, 170°C or higher and 2.5 parts by weight or more are particularly preferred, 170°C or higher and 3.0 parts by weight or more are particularly preferred, and 170°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 180°C or higher and 0.5 parts by weight or more are preferred, 180°C or higher and 1.0 parts by weight or more are more preferred, 180°C or higher and 1.6 parts by weight or more are even more preferred, 180°C or higher and 2.0 parts by weight or more are even more preferred, 180°C or higher and 2.5 parts by weight or more are particularly preferred, 180°C or higher and 3.0 parts by weight or more are particularly preferred, and 180°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 200°C or higher and 0.5 parts by weight or more are preferred, 200°C or higher and 1.0 parts by weight or more are more preferred, 200°C or higher and 1.6 parts by weight or more are even more preferred, 200°C or higher and 2.0 parts by weight or more are even more preferred, 200°C or higher and 2.5 parts by weight or more are particularly preferred, 200°C or higher and 3.0 parts by weight or more are particularly preferred, and 200°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 210°C or higher and 0.5 parts by weight or more are preferred, 210°C or higher and 1.0 parts by weight or more are more preferred, 210°C or higher and 1.6 parts by weight or more are even more preferred, 210°C or higher and 2.0 parts by weight or more are even more preferred, 210°C or higher and 2.5 parts by weight or more are particularly preferred, 210°C or higher and 3.0 parts by weight or more are particularly preferred, and 210°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 220°C or higher and 0.5 parts by weight or more are preferred, 220°C or higher and 1.0 parts by weight or more are more preferred, 220°C or higher and 1.6 parts by weight or more are even more preferred, 220°C or higher and 2.0 parts by weight or more are even more preferred, 220°C or higher and 2.5 parts by weight or more are particularly preferred, 220°C or higher and 3.0 parts by weight or more are particularly preferred, and 220°C or higher and 5.0 parts by weight or more are most preferred. Furthermore, 230°C or higher and 0.5 parts by weight or more are preferred, 230°C or higher and 1.0 parts by weight or more are more preferred, 230°C or higher and 1.6 parts by weight or more are even more preferred, 230°C or higher and 2.0 parts by weight or more are even more preferred, 230°C or higher and 2.5 parts by weight or more are particularly preferred, 230°C or higher and 3.0 parts by weight or more are particularly preferred, and 230°C or higher and 5.0 parts by weight or more are most preferred. The heat treatment temperature in the above combination is preferably 310°C or less, more preferably 300°C or less, even more preferably 290°C or less, even more preferably 280°C or less, especially preferably 270°C or less, particularly preferably 250°C or less, and most preferably 240°C or less. The amount of the fluorine radical source added in the above combination is, in terms of fluorine atoms, preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, even more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less, relative to 100 parts by weight of the raw material PTFE. The upper limit of the combination of the heat treatment temperature and the amount of the fluorine radical source is preferably 240°C or less and 35.0 parts by weight or less, more preferably 240°C or less and 26.0 parts by weight or less, even more preferably 240°C or less and 20.0 parts by weight or less, and particularly preferably 240°C or less and 15.0 parts by weight or less.

[0065] The amount (parts by weight) of the fluorine radical source added relative to 100 parts by weight of PTFE was calculated according to the following formula. A = (B / F) × 100 B=C×D×E C = {P / (RT × 1000)} × G × H A: Amount of fluorine radical source added (parts by weight) per 100 parts by weight of PTFE B: Total amount of fluorine radical source added (g) C: Fluorine radical source concentration in the mixed gas (g / mL) D: Mixed gas flow rate (mL / min) E: Fluorination treatment time (min) F: Sample filling amount (g) G: Molecular weight of the fluorine radical source (g / mol) H: Ratio of fluorine radical source in the mixed gas In the above formula, P, R, and T are as follows: P = pressure (atm) R = 0.082 (atm L / K mol) T=temperature (K)

[0066] Any reactor equipped with a heating device and capable of sufficient solid-gas contact can be used for the fluorination treatment. Specific examples include fluidized bed and tray-type solid-gas contact reactors.

[0067] In the method for producing the modified PTFE powder, the removal step may be carried out multiple times. For example, the removal step may be carried out 2, 3, 4, 5, 6, 7, 8, 9, or 10 times. The heat treatment and fluorination treatment may be carried out in combination or simultaneously.

[0068] The method for washing with water or an organic solvent is not particularly limited, and any conventionally known method can be used.

[0069] When a PTFE powder is obtained using a hydrocarbon surfactant, compounds represented by the general formulas (1) and (2) may be produced in an amount of 1 to 200 ppm relative to the PTFE. By the above-mentioned removal step, the compound represented by the general formula (1) or (2) in the PTFE aqueous dispersion is removed or reduced, and a modified PTFE powder can be obtained.

[0070] The removal step preferably removes 80% by mass or more of the compounds represented by general formulas (1) and (2) in the PTFE powder, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, especially preferably 97% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass or more. The removal step is preferably carried out so that the content of the compounds represented by the general formulas (1) and (2) in the resulting modified PTFE powder is 500 ppb or less, more preferably 200 ppb or less, even more preferably 100 ppb or less, particularly preferably 50 ppb or less, and most preferably 25 ppb or less, relative to PTFE.

[0071] The present invention is a method for producing a molded article using PTFE produced using a hydrocarbon surfactant, the method comprising the step of removing or reducing a compound represented by the following general formula (1) or (2): General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. The metal atom may be a monovalent or divalent metal atom, such as an alkali metal (Group 1) or alkaline earth metal (Group 2), and specific examples include Na, K, and Li. Above R 5 The four R's 5 may be the same or different. 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. In the general formula (1), m may be 5 to 11. In the general formula (2), n may be 6 to 12.

[0072] As the PTFE produced using a hydrocarbon surfactant, the PTFE powder obtained using the above-mentioned hydrocarbon surfactant can be used. As the PTFE, PTFE such as homo-PTFE and modified PTFE described in the method for producing a purified PTFE aqueous dispersion can be used.

[0073] In the method for producing a molded article of the present invention, methods for removing or reducing the compound represented by general formula (1) or (2) include heat treatment, fluorination treatment, and the like.

[0074] The heat treatment method is not particularly limited, and any conventionally known method can be used. The heat treatment temperature is preferably 150°C or higher. The heat treatment temperature is more preferably 160°C or higher. That is, the removal step preferably includes a step of heat treatment at a temperature of 160°C or higher. The temperature of the heat treatment is more preferably 170°C or higher, even more preferably 180°C or higher, even more preferably 200°C or higher, particularly preferably 210°C or higher, particularly preferably 220°C or higher, and most preferably 230°C or higher. The temperature of the heat treatment is preferably 310°C or less, more preferably 300°C or less, even more preferably 290°C or less, even more preferably 280°C or less, and most preferably 270°C or less. The time for the heat treatment is not particularly limited, but is, for example, 1 minute or more and 24 hours or less. The heat treatment may be accompanied by drying, which reduces the amount of the compound represented by general formula (1) or (2) and the compound represented by general formula (7) described below.

[0075] The fluorination treatment can be carried out by a conventional method. For example, the PTFE powder can be exposed to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions. Fluorine radical sources include fluorine gas, CoF, AgF, UF, OF, NF, CF, OF, and halogen fluorides such as IF, ClF, and BrF. Since the reaction with the fluorine radical source is highly exothermic, the fluorine radical source may be diluted with an inert gas such as nitrogen. The level of fluorine radical source in the fluorine radical source / inert gas mixture can be from 1 to 100% by volume, but is preferably from about 5 to about 25% by volume due to the high hazards of working with pure fluorine. For fluoropolymer resins that exhibit severe thermally induced discoloration, the fluorine radical source / inert gas mixture may be sufficiently diluted to prevent overheating of the fluoropolymer and the attendant fire hazard. The heat treatment and fluorination treatment may be carried out in combination or simultaneously. The fluorination treatment reduces the compounds represented by general formula (1) or (2) and the compounds represented by general formula (7) described below.

[0076] The method of the fluorination treatment is not particularly limited, and conventionally known methods can be used. The temperature of the fluorination treatment is preferably above 100°C. The temperature of the fluorination treatment is more preferably 110°C or higher, even more preferably 120°C or higher, even more preferably 130°C or higher, and especially preferably 150°C or higher. Furthermore, it is particularly preferably 170°C or higher, even more preferably 180°C or higher, even more preferably 200°C or higher, especially preferably 210°C or higher, especially preferably 220°C or higher, and most preferably 230°C or higher. Furthermore, the temperature of the fluorination treatment is preferably 310°C or lower, more preferably 300°C or lower, even more preferably 290°C or lower, even more preferably 280°C or lower, especially preferably 270°C or lower, especially preferably 250°C or lower, and most preferably 240°C or lower. The time for the fluorination treatment is not particularly limited, but is, for example, 1 minute or more and 24 hours or less.

[0077] In the above-mentioned fluorination treatment, the amount of the fluorine radical source added, in terms of fluorine atoms, is preferably 0.5 parts by weight or more, more preferably 0.8 parts by weight or more, and even more preferably 1.0 parts by weight or more, relative to 100 parts by weight of the raw material PTFE. Also, it is more preferably 1.6 parts by weight or more, even more preferably 2.0 parts by weight or more, even more preferably 2.5 parts by weight or more, especially preferably 3.0 parts by weight or more, and particularly preferably 5.0 parts by weight or more. Also, the amount of the fluorine radical source added is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, even more preferably 20.0 parts by weight or less, and especially preferably 15.0 parts by weight or less. If the amount of the fluorine radical source added is too small, the removal or reduction of the compound represented by general formula (1) or (2) may be insufficient. Furthermore, the removal or reduction of unidentifiable compounds may be insufficient. If the amount of the fluorine radical source added is too large, the fluorination effect will not be improved, and this may be uneconomical. In the fluorination treatment in the method for producing a molded article, all of the combinations of the temperature of the fluorination treatment and the content of the fluorine radical source in the method for producing a PTFE powder described above can be used.

[0078] Any reactor equipped with a heating device and capable of sufficient solid-gas contact can be used for the fluorination treatment. Specific examples include fluidized bed and tray-type solid-gas contact reactors.

[0079] The method for producing a molded article of the present invention may be any method as long as it includes the above-mentioned removing step.

[0080] In addition to the above-mentioned removal step, the method for producing a molded product of the present invention may further include the steps of: (1a) mixing the PTFE powder obtained using a hydrocarbon surfactant with an extrusion aid; (1b) paste-extrusion molding the resulting mixture; (1c) drying the extrudates obtained by extrusion molding; and (1d) calcining the dried extrudates to obtain a molded product. The removal step may be performed after step (1a) and before step (1b), after step (1b) and before step (1c), or after step (1d). When a heat treatment is performed as a removal step after step (1d), the heat treatment temperature may be above 310°C, and in that case, the heat treatment is preferably performed at 500°C or less. The removal step may be carried out during step (1b), step (1c), or step (1d). The removal step may be carried out multiple times. For example, the removal step may be carried out two, three, four, five, six, seven, eight, nine, or ten times. The heat treatment and fluorination treatment may be carried out in combination or simultaneously. As described above, in the method for producing a molded article of the present invention, the removal step may be a step of removing or reducing the compound represented by general formula (1) or (2) from the PTFE powder obtained by using a hydrocarbon-based surfactant, or a step of removing or reducing the compound represented by general formula (1) or (2) from a molded article molded using the PTFE powder obtained by using a hydrocarbon-based surfactant.

[0081] The paste extrusion molding can be carried out by a conventionally known method, and molding conditions can be selected depending on the desired shape and size. The paste extrusion molding can also be carried out by adding conventionally known additives such as pigments and fillers to the PTFE powder.

[0082] In addition to the above-mentioned removing step, the method for producing a molded article of the present invention may further include the steps of: (2a) mixing the PTFE powder obtained using a hydrocarbon surfactant with an extrusion aid; (2b) extrusion-rolling the resulting mixture; (2c) drying the extrudate obtained by extrusion-rolling; (2d) uniaxially stretching the dried extrudate; (2e) biaxially stretching the uniaxially stretched extrudate; (2f) firing the biaxially stretched extrudate; and (2g) laminating the fired extrudate with another material. In this case, the removing step may be performed after step (2a) and before step (2b), after step (2b) and before step (2c), after step (2c) and before step (2d), after step (2d) and before step (2e), after step (2e) and before step (2f), or after step (2f) and before step (2g). The removal step may be carried out during step (2a), (2b), (2c), (2d), (2e), (2f), or (2g). The removal step may be carried out multiple times. The heat treatment and the fluorination treatment may be carried out in combination or simultaneously.

[0083] The extrusion aid is not particularly limited, and any commonly known extrusion aid can be used, such as hydrocarbon oil.

[0084] The method for producing a molded article of the present invention may include, in addition to the above-mentioned removing step, a step of compression molding the PTFE powder obtained using a hydrocarbon surfactant. In this case, the above-mentioned removing step may be carried out during or after the compression molding step. The above-mentioned removing step may be carried out multiple times. A heat treatment and a fluorination treatment may be carried out in combination.

[0085] In the method for producing a molded body of the present invention, the removal step preferably removes 80% by mass or more of the compounds represented by general formulas (1) and (2) before and after the removal step, more preferably removes 85% by mass or more, even more preferably removes 90% by mass or more, even more preferably removes 95% by mass or more, especially preferably removes 97% by mass or more, particularly preferably removes 98% by mass or more, and most preferably removes 99% by mass or more. The removal step is preferably carried out so that the content of the compounds represented by the general formulas (1) and (2) in the obtained PTFE molded article is 500 ppb or less, more preferably 200 ppb or less, even more preferably 100 ppb or less, particularly preferably 50 ppb or less, and most preferably 25 ppb or less, relative to PTFE.

[0086] As described above, one of the preferred methods for removing or reducing the compound represented by general formula (1) or (2) is a fluorination treatment carried out at a specific temperature. That is, the present invention also relates to a method for producing modified PTFE, which comprises a step of contacting PTFE obtained using a hydrocarbon surfactant with a fluorine radical source at a temperature exceeding 100°C to remove or reduce the compound represented by the following general formula (1) or (2): General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. By contacting the fluorine radical source at the above-mentioned specific temperature (fluorination treatment), the compound represented by general formula (1) or (2) can be efficiently removed. Furthermore, PTFE obtained using a hydrocarbon surfactant may contain impurities such as decomposition products of substances used in the polymerization of PTFE, in addition to the compound represented by general formula (1) or (2). However, such impurities can also be removed by contacting the PTFE with a fluorine radical source at the above-mentioned specific temperature. The temperature when the fluorine radical source is contacted is above 100°C. The temperature when the fluorine radical source is contacted can be adjusted by a conventionally known method, and is preferably 110°C or higher, more preferably 120°C or higher, even more preferably 130°C or higher, even more preferably 150°C or higher, especially more preferably 170°C or higher, more preferably 180°C or higher, and particularly preferably 200°C or higher. Also, 210°C or higher is more preferred, especially preferably 220°C or higher, and most preferably 230°C or higher. Also, the temperature is preferably 310°C or lower, more preferably 300°C or lower, even more preferably 290°C or lower, even more preferably 280°C or lower, especially preferably 270°C or lower, especially preferably 250°C or lower, and most preferably 240°C or lower. In this manufacturing method, all of the above-mentioned combinations of the amount of fluorine radical source added and the temperature and amount added can be used. When a fluorine radical source is contacted in the above-mentioned method for producing modified PTFE, various conditions for the fluorination treatment described in the above-mentioned methods for producing modified PTFE powder and for producing a molded body (e.g., the type of fluorine radical source, the amount of fluorine radical source added, the timing and number of times of fluorination treatment, etc.) can be appropriately adopted. Furthermore, in addition to the method of contacting a fluorine radical source, the removal methods described in the removal step, such as heat treatment and washing with water or an organic solvent, may be combined. In particular, a heat treatment step may be performed after the step of contacting a fluorine radical source to remove or reduce the compound represented by general formula (1) or (2). By performing the heat treatment step, the content of the compounds represented by general formulas (1) and (2) can be further reduced. Furthermore, the content of the compound represented by general formula (7) can also be further reduced. The temperature and time for the heat treatment step can be within the ranges described above. In the above-mentioned method for producing modified PTFE, the PTFE obtained by using the above-mentioned hydrocarbon surfactant may be in the form of a powder or a molded article.

[0087] As described above, a fluorination treatment using a specific amount of a fluorine radical source is also one of the preferred methods for removing or reducing the compound represented by general formula (1) or (2). That is, the present invention also provides a method for producing PTFE, which comprises a step of contacting PTFE obtained using a hydrocarbon surfactant with a fluorine radical source to remove or reduce the compound represented by the following general formula (1) or (2), and is characterized in that the amount of the fluorine radical source added is 0.5 parts by weight or more per 100 parts by weight of PTFE, calculated as fluorine atoms: General formula (1):(H-(CF2) m -COO) p M 1 (wherein m is 3 to 19, M 1 is H, metal atom, NR 5 4(R 5may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. p is 1 or 2. General formula (2):(H-(CF2) n -SO3) q M 2 (wherein n is 4 to 20. M 2 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. q is 1 or 2. By contacting the fluorine radical source in the specific amount added (fluorination treatment), the compound represented by general formula (1) or (2) can be efficiently removed. Furthermore, PTFE obtained using a hydrocarbon surfactant may contain impurities such as decomposition products of substances used in the polymerization of PTFE, in addition to the compound represented by general formula (1) or (2). However, such impurities can also be removed by contacting the PTFE with a fluorine radical source in the above-mentioned specific amount. The amount of the fluorine radical source added is 0.5 parts by weight or more, calculated as fluorine atoms, per 100 parts by weight of the raw material PTFE. It is preferably 0.8 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 1.6 parts by weight or more, more preferably 2.0 parts by weight or more, even more preferably 2.5 parts by weight or more, still more preferably 3.0 parts by weight or more, and particularly preferably 5.0 parts by weight or more. The amount of the fluorine radical source added is preferably 35.0 parts by weight or less, more preferably 26.0 parts by weight or less, even more preferably 20.0 parts by weight or less, and particularly preferably 15.0 parts by weight or less. If the amount of the fluorine radical source added is too small, the removal or reduction of the compound represented by general formula (1) or (2) may be insufficient. Furthermore, the removal or reduction of unidentifiable compounds may be insufficient. If the amount of the fluorine radical source added is too large, the fluorination effect will not be improved, and the process tends to be uneconomical. In this manufacturing method, the fluorination treatment temperature and the combination of temperature and amount of addition can all be used as described above. When a fluorine radical source is brought into contact in the above-mentioned method for producing modified PTFE, various conditions (e.g., type of fluorine radical source, temperature of fluorination treatment, timing and number of times of fluorination treatment, etc.) explained in the above-mentioned method for producing modified PTFE powder and method for producing a molded body can be appropriately adopted. Furthermore, in addition to the method of contacting with a fluorine radical source, the removal methods described in the removal step, such as heat treatment and washing with water or an organic solvent, may be combined. In particular, a heat treatment step may be performed after the step of contacting with a fluorine radical source to remove or reduce the compound represented by general formula (1) or (2). By performing the heat treatment step, the content of the compounds represented by general formulas (1) and (2) can be further reduced. Furthermore, the content of the compound represented by general formula (7) can also be further reduced. The temperature and time of the heat treatment step can be within the ranges described above. In the above-mentioned method for producing modified PTFE, the PTFE obtained by using the above-mentioned hydrocarbon surfactant may be in the form of a powder or a molded article.

[0088] Specific hydrocarbon surfactants are described below.

[0089] Hydrocarbon surfactants have a hydrophilic portion and a hydrophobic portion on the same molecule and can be cationic, nonionic, or anionic.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] Examples of nonionic hydrocarbon surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

[0094] Specific examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene behenyl ether.

[0095] Specific examples of polyoxyethylene alkylphenyl ethers include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

[0096] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, and polyethylene glycol monostearate.

[0097] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0098] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0099] Specific examples of glycerol esters include glycerol monomyristate, glycerol monostearate, and glycerol monooleate.

[0100] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

[0101] The ethers and esters may have an HLB value of 10-18.

[0102] Examples of nonionic hydrocarbon 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), T-Det series (A138), and Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10), all manufactured by BASF.

[0103] 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.

[0104] As a hydrocarbon surfactant, RLM 1 (In the formula, 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 may be a cyclic ring. L is -ArSO3 - , -SO3 - , -SO4-, -PO3 - or -COO - and M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate. ) Specifically, CH3-(CH2) n -LM 1(wherein n is an integer of 6 to 17, and L and M are the same as above). Mixtures where R is an alkyl group having 12 to 16 carbon atoms and L is sulfate or sodium dodecyl sulfate (SDS) can also be used. Hydrocarbon surfactants include R 6 (-LM 1 )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 alkylene group has three or more carbon atoms, it may contain a monovalent or divalent heterocycle or may be a cyclic ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M 1 is H, metal atom, NR 5 4(R 5 may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate. ) Hydrocarbon surfactants include R 7 (-LM 1 )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 alkylidyne group has three or more carbon atoms, it may contain a monovalent or divalent heterocycle or may be a cyclic ring. - , -SO3 - , -SO4-, -PO3 - or -COO - and M 1 is H, metal atom, NR 5 4(R 5may be the same or different and are H or an organic group having 1 to 10 carbon atoms), imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. -ArSO3 - is an aryl sulfonate. )

[0105] 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.

[0106] The hydrophilic portion of the siloxane surfactant may comprise one or more polar moieties containing ionic groups such as sulfate, sulfonate, phosphonate, phosphate ester, carboxylate, carbonate, sulfosuccinate, taurate (as free acid, salt or ester), phosphine oxide, betaine, betaine copolyol, quaternary ammonium salt, etc. The ionic hydrophobic portion may also comprise an ionically functionalized siloxane graft. Such siloxane surfactants include, for example, 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.

[0107] The hydrophilic portion of the siloxane 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 invention are siloxanes having nonionic moieties, i.e., nonionic siloxane surfactants.

[0108] The arrangement of hydrophobic and hydrophilic portions of the siloxane surfactant structure may take the form of a diblock polymer (AB), a triblock polymer (ABA) (where "B" represents the siloxane portion of the molecule), or a multiblock polymer. Alternatively, the siloxane surfactant may comprise a graft polymer.

[0109] Siloxane surfactants are also disclosed in US Pat. No. 6,841,616.

[0110] Siloxane-based anionic hydrocarbon surfactants include SilSense, available from Noveon® Consumer Specialties of Lubrizol Advanced Materials, Inc. TM PE-100 Silicone, SilSense TM CA-1 silicone and the like.

[0111] Anionic hydrocarbon surfactants also include the sulfosuccinate surfactant Lankropol® K8300 from Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate hydrocarbon surfactants include sodium diisodecyl sulfosuccinate (Emulsogen® SB10 from Clariant) and sodium diisotridecyl sulfosuccinate (Polirol® TR / LNA from Cesapinia Chemicals).

[0112] The hydrocarbon surfactants include PolyFox® surfactants from Omnova Solutions, Inc. TM PF-156A, PolyFox TM PF-136A, etc.)

[0113] The hydrocarbon surfactant may be a surfactant represented by the following general formula (1): [ka] (In the formula, R 1 ~R 5 represents H or a monovalent substituent, provided that R 1 and R 3 At least one of the groups has the general formula: -YR 6 a group represented by R 2 and R 5 At least one of the groups is a group represented by the general formula: -XA or a group represented by the general formula: -YR 6 represents a group represented by the following formula: Furthermore, X, in each occurrence, is the same or different and represents a divalent linking group or a bond; A is the same or different in each occurrence and is -COOM, -SO3M, or -OSO3M (M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group); Y may be the same or different in each occurrence and may be -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 a divalent linking group selected from the group consisting of CO—, or a bond, R 8 is H or an organic group; R 6 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 1 ~R 5 Any two of these may be bonded to each other to form a ring.) (hereinafter also referred to as surfactant (1)).

[0114] The surfactant (1) will be explained.

[0115] In the formula, R 1 ~R 5 represents H or a monovalent substituent, provided that R 1 and R 3 At least one of the groups has the general formula: -YR 6 a group represented by R 2 and R 5 At least one of the groups is a group represented by the general formula: -XA or a group represented by the general formula: -YR 6 R represents a group represented by 1 ~R 5 Any two of these may be bonded to each other to form a ring.

[0116] R 1 The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0117] R 1 The alkyl group as above preferably does not contain a carbonyl group. The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms. The alkyl group preferably does not have any substituents.

[0118] R 1 As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not contain a substituent is even more preferred, a methyl group (-CH3) or an ethyl group (-C2H5) is particularly preferred, and a methyl group (-CH3) is most preferred.

[0119] The monovalent substituent includes a group represented by the general formula: -YR 6 a group represented by the general formula: -XA; -H; optionally substituted C 1-20 Alkyl groups, -NH2, -NHR 9 (R 9 is an organic group), -OH, -COOR 9 (R 9 is an organic group) or -OR 9 (R 9 is an organic group). The alkyl group preferably has 1 to 10 carbon atoms.

[0120] R 9 As for C 1-10 or C 1-10 The alkylcarbonyl group of C is preferred. 1-4 or C 1-4 An alkylcarbonyl group of the formula is more preferred.

[0121] In the formula, X may be the same or different in each occurrence and represents a divalent linking group or bond. R 6 When X does not contain any of a carbonyl group, an ester group, an amide group, and a sulfonyl group, X is preferably a divalent linking group containing at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0122] X may be -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, or -CONR 8 - and -NR 8 a divalent linking group containing at least one bond selected from the group consisting of CO—, C 1-10 An alkylene group or a bond represented by the formula R 8 represents H or an organic group.

[0123] R 8 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferred, and H is even more preferred.

[0124] In the formula, A is the same or different in each occurrence and is -COOM, -SO3M, or -OSO3M (M is H, a metal atom, NR 7 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent, R 7 is H or an organic group. 7 may be the same or different.

[0125] 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 preferred. 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.

[0126] M is H, a metal atom, or NR 7 4 is preferred, H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 7 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, Na, K or NH4 is even more preferred, Na or NH4 is particularly preferred, and NH4 is most preferred.

[0127] In the formula, Y may be the same or different in each occurrence and may be -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 a divalent linking group selected from the group consisting of CO—, or a bond, R 8 represents H or an organic group.

[0128] Y is a bond, -O-, -COO-, -OCO-, -CONR 8 - and -NR 8 A divalent linking group selected from the group consisting of -CO- is preferred, and a divalent linking group selected from the group consisting of a bond, -COO-, and -OCO- is more preferred.

[0129] R 8 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferred, and H is even more preferred.

[0130] In the formula, R 6 In each occurrence, R may be the same or different and represent an alkyl group having two or more carbon atoms which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon atoms. 6 The organic group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.

[0131] R 6 The alkyl group of R may contain one or more groups selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms, but does not contain these groups at the terminal of the alkyl group. 6In 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.

[0132] R 6 As for General formula:-R 10 -CO-R 11 a group represented by General formula:-R 10 -COO-R 11 a group represented by General formula:-R 11 a group represented by General formula:-R 10 -NR 8 CO-R 11 or a group represented by General formula:-R 10 -CONR 8 -R 11 a group represented by (In the formula, R 8 represents H or an organic group. 10 is an alkylene group, R 11 is preferably an alkyl group which may have a substituent. R 6 As the general formula: -R 10 -CO-R 11 A group represented by the following formula is more preferred.

[0133] R 8 As for H or C 1-10 is preferably an organic group represented by the formula: 1-4 The organic group is more preferred, and H is even more preferred.

[0134] R 10 The number of carbon atoms in the alkylene group 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. 10The 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.

[0135] R 11 The number of carbon atoms in the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 6, even more preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. 11 The alkyl group of R is preferably composed of only primary, secondary, and tertiary carbon atoms, and particularly preferably composed of only primary and secondary carbon atoms. 11 As the alkyl group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, and a methyl group is most preferred.

[0136] The surfactant (1) is preferably a compound represented by general formula (1-1), a compound represented by general formula (1-2), or a compound represented by general formula (1-3), and more preferably a compound represented by general formula (1-1) or a compound represented by general formula (1-2).

[0137] General formula (1-1): [ka] (In the formula, R 3 ~R 6 , X, A and Y are as above.)

[0138] General formula (1-2): [ka] (In the formula, R 4 ~R 6 , X, A and Y are as above.)

[0139] General formula (1-3): [ka] (In the formula, R 2 , R 4~R 6 , X, A and Y are as above.)

[0140] Examples of the group represented by the general formula -XA include: -COOM, -R 12 COOM, -SO3M, -OSO3M, -R 12 SO3M, -R 12 OSO3M, -OCO-R 12 -COOM, -OCO-R 12 -SO3M, -OCO-R 12 -OSO3M -COO-R 12 -COOM, -COO-R 12 -SO3M, -COO-R 12 -OSO3M, -CONR 8 -R 12 -COOM, -CONR 8 -R 12 -SO3M, -CONR 8 -R 12 -OSO3M, -NR 8 CO-R 12 -COOM, -NR 8 CO-R 12 -SO3M, -NR 8 CO-R 12 -OSO3M, -OS(=O)2-R 12 -COOM, -OS(=O)2-R 12 -SO3M, or -OS(=O)2-R 12 -OSO3M (In the formula, R 8 and M are as above. 12 is C 1-10An alkylene group represented by the formula: is preferred. Above R 12 In the alkylene group, 75% or less of the hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, or 25% or less may be substituted with halogen atoms, but it is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0141] General formula:-YR 6 Examples of the group represented by the formula: General formula:-R 10 -CO-R 11 a group represented by General formula:-OCO-R 10 -CO-R 11 a group represented by General formula:-COO-R 10 -CO-R 11 a group represented by General formula:-OCO-R 10 -COO-R 11 a group represented by General formula:-COO-R 11 a group represented by the group represented by General formula:-NR 8 CO-R 10 -CO-R 11 or a group represented by General formula:-CONR 8 -R 10 -NR 8 CO-R 11 A group represented by (In the formula, R 8 , R 10 and R 11 is as described above.) is preferred.

[0142] In the formula, R 4 and R 5 are independently H or C 1-4 The alkyl groups are preferably: Above R 4 and R 5In 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.

[0143] R in general formula (1-1) 3 is H or optionally substituted C 1-20 The alkyl group is preferably H or unsubstituted C 1-20 An alkyl group represented by the formula (I) is more preferred, and H is even more preferred. Above R 3 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.

[0144] R in general formula (1-3) 2 is H, OH or optionally substituted C 1-20 The alkyl group having no H, OH or substituent is preferably C 1-20 An alkyl group such as the above is more preferred, and H or OH is even more preferred. Above R 2 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.

[0145] The surfactant (1) is represented by the formula: R 6 -COOH(where R 6 is as described above.) is reacted with a halogenating agent to give a compound represented by the formula: R 6 -COZ(in the formula, R 6is as described above. Z is a halogen atom.), and the carboxylic acid halide and a compound of the formula: [ka] (In the formula, R 3 ~R 5 , X and A are as described above. Z 11 is —CHO—, —O— or —NH—.) to form a compound represented by the formula: [ka] (In the formula, R 3 ~R 6 , X, A and Z 11 can be suitably produced by a production method including step (12) of obtaining compound (12) represented by the formula (12) as described above.

[0146] R in the formula of the above acid compound 3 As the general formula: -Z 11 H (where Z 11 is as defined above.) or -H is preferred. R 3 is the general formula: -Z 11 In the case where the group is a group represented by H, in step (12), the group is reacted with the carboxylic acid halide to form a compound of the general formula: -Z 11 -CO-R 6 (In the formula, R 6 and Z 11 is as above.) A group represented by the formula is produced.

[0147] Examples of the halogenating agent used in step (11) include oxalyl chloride, thionyl chloride, diethylaminosulfur trifluoride (DAST), Deoxo-Fluor, and 1,1,2,2-tetrafluoro-N,N-dimethylethylamine (TFEDMA).

[0148] Z is preferably F or Cl, more preferably Cl.

[0149] In step (11), the reaction ratio of the carboxylic acid and the halogenating agent is preferably 0.6 to 5.0 mol, more preferably 0.8 to 2.0 mol, and more preferably 0.5 to 10 mol, more preferably 0.6 to 5.0 mol, per 1 mol of the carboxylic acid, in consideration of improving yield and reducing waste.

[0150] The reaction in step (11) can be carried out in a solvent, such as an ester, a ketone, an aromatic hydrocarbon, an ether, a nitrogen-containing polar organic compound, a halogenated hydrocarbon, a nitrile, pyridine, or a mixture thereof.

[0151] 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.

[0152] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0153] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0154] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0155] 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.

[0156] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0157] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0158] The reaction temperature in step (11) is preferably 0 to 150°C, more preferably 20 to 100°C, and preferably -78 to 150°C, more preferably 0 to 100°C.

[0159] The reaction pressure in step (11) is preferably 0 to 5 MPa, more preferably 0.1 to 1.0 MPa.

[0160] The reaction time in step (11) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0161] In the step (12), the reaction ratio of the carboxylic acid halide and the acid compound is preferably 0.5 to 10 mol, more preferably 0.6 to 5.0 mol, and even more preferably 0.8 to 2.0 mol, of the acid compound relative to 1 mol of the carboxylic acid halide, in consideration of improving the yield and reducing waste.

[0162] The reaction in step (12) is preferably carried out in the presence of an acid, such as sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, with sulfuric acid being preferred.

[0163] In consideration of improving the yield and reducing waste, the amount of the acid used in step (12) is preferably 0.00001 to 1.0 mol, more preferably 0.0001 to 1.0 mol, still more preferably 0.00005 to 0.1 mol, and particularly preferably 0.001 to 0.1 mol, per 1 mol of the carboxylic acid halide.

[0164] The reaction temperature in step (12) is preferably 0 to 150°C, more preferably 20 to 100°C.

[0165] The reaction pressure in step (12) is preferably 0 to 5 MPa, more preferably 0.1 to 1.0 MPa.

[0166] The reaction time in step (12) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0167] The surfactant (1) may also be represented by the formula: [ka] (In the formula, R 1 ~R 5 is as above. Z 11 is —CHO—, —O— or —NH—.) and a compound (20) represented by the formula: [ka] (wherein n is an integer of 1 to 5) to form a compound represented by the formula: [ka] (In the formula, R 1 ~R 5 , Z 11 , M and n are as defined above. The compound (21) can be suitably produced by a production method including a step (21) of obtaining a compound (21) represented by the formula:

[0168] R in the formula of compound (20) 2 As the general formula: -Z 11 H (where Z 11is as defined above.) or -H is preferred. R 2 is the general formula: -Z 11 In the case where the group is a group represented by H, in step (21), the group is reacted with the acid anhydride to form a compound of the general formula: -Z 11 -CO-(CH2) n -COOM(in the formula, Z 11 , M and n are as defined above.) is generated. Compound (20) may be a hydrochloride, sulfate, or the like, as long as it contains the structure represented by the above formula.

[0169] In the step (21), the reaction ratio of compound (20) and the acid anhydride is preferably 0.5 to 10 mol, more preferably 0.6 to 5.0 mol, still more preferably 1.2 to 10 mol, and particularly preferably 1.6 to 4.0 mol, of the acid anhydride relative to 1 mol of compound (20), in consideration of improving the yield and reducing waste.

[0170] The reaction in step (21) can be carried out in the presence of a base.

[0171] Examples of the base include amines, potassium hydroxide, sodium hydroxide, and potassium carbonate.

[0172] Examples of the amine 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, with pyridine or triethylamine being preferred.

[0173] The reaction temperature in step (21) is preferably 0 to 150°C, more preferably 20 to 80°C, and preferably -78 to 150°C, more preferably 0 to 100°C.

[0174] The reaction pressure in step (21) is preferably 0 to 5 MPa, more preferably 0.1 to 1 MPa.

[0175] The reaction time in step (21) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0176] The surfactant (1) may also be represented by the formula: [ka] (In the formula, R 4 and R 5 is as above.) and a tartaric acid ester represented by the formula: R 6 R 8 -NH(wherein, R 6 and R 8 is as described above.) to react with an amine represented by the formula: [ka] (In the formula, R 4 ~R 6 and R 8 as defined above.) and Compound (31) and the formula: [ka] (wherein M is as defined above) to react with a sulfonic acid chloride represented by the formula: [ka] (In the formula, R 4 ~R 6 , R 8 and M is as defined above.) to obtain a compound (32).

[0177] In step (31), the reaction ratio of the tartaric acid ester to the amine is preferably 0.5 to 10 mol, more preferably 0.6 to 5.0 mol, even more preferably 1.2 to 5 mol, and particularly preferably 1.6 to 5.0 mol, relative to 1 mol of the tartaric acid ester, in consideration of improving yield and reducing waste.

[0178] The reaction in step (31) can be carried out in a solvent, preferably an organic solvent, more preferably an alcohol, an ether, a halogenated hydrocarbon, a nitrogen-containing polar organic compound, or a nitrile.

[0179] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0180] Examples of the ether include tetrahydrofuran, dioxane, and diethylene glycol diethyl ether.

[0181] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene.

[0182] 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.

[0183] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile.

[0184] The reaction temperature in step (31) is preferably 0 to 150°C, more preferably 20 to 100°C.

[0185] The reaction pressure in step (31) is preferably 0 to 5 MPa, more preferably 0.1 to 1 MPa.

[0186] The reaction time in step (31) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0187] In the step (32), the reaction ratio of compound (31) and the sulfonic chloride is preferably 1.0 to 50 mol, more preferably 1.6 to 20 mol, of the sulfonic chloride relative to 1 mol of compound (31), in consideration of improving the yield and reducing waste.

[0188] The reaction in step (32) 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.

[0189] Examples of the amine in step (32) 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 is preferred.

[0190] The amount of the base used in step (32) is preferably 0.1 to 50 mol, more preferably 1.0 to 20 mol, per 1 mol of compound (31), in consideration of improving yield and reducing waste.

[0191] The reaction in step (32) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably a nitrile, a halogenated hydrocarbon, dimethyl sulfoxide, sulfolane, a nitrogen-containing polar organic compound, or an ether.

[0192] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0193] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0194] 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.

[0195] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether is preferred.

[0196] The reaction temperature in step (32) is preferably from -78 to 150°C, more preferably from -78 to 100°C, even more preferably from -20 to 100°C, and particularly preferably from 10 to 50°C.

[0197] The reaction pressure in step (32) is preferably 0 to 5 MPa, more preferably 0.1 to 1.0 Pa.

[0198] The reaction time in step (32) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0199] The surfactant (1) may also be represented by the formula: [ka] (In the formula, R 1 and R 3 ~R 5is as above.) and an alcohol represented by the formula: [ka] (wherein n is an integer of 1 to 5) to form a compound represented by the formula: [ka] (In the formula, R 1 , R 3 ~R 5 , M and n are as defined above.

[0200] In the step (41), the reaction ratio of the alcohol and the acid anhydride is preferably 0.5 to 10 mol, more preferably 0.6 to 4.0 mol, still more preferably 1.2 to 4.0 mol, and particularly preferably 1.6 to 4.0 mol, relative to 1 mol of the alcohol, in consideration of improving yield and reducing waste.

[0201] The reaction in step (41) can be carried out in the presence of a base.

[0202] Examples of the base include amines, potassium hydroxide, sodium hydroxide, and potassium carbonate.

[0203] Examples of the amine 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, with pyridine or triethylamine being preferred.

[0204] The reaction temperature in step (41) is preferably from -78 to 150°C, more preferably from 0 to 150°C, even more preferably from 0 to 100°C, and particularly preferably from 20 to 80°C.

[0205] The reaction pressure in the step (41) is preferably 0 to 5 MPa, more preferably 0.1 to 1 MPa.

[0206] The reaction time in step (41) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0207] The surfactant (1) may also be represented by the formula: [ka] (In the formula, R 4 and R 5 is as above.) and a tartaric acid ester represented by the formula: R 6 R 8 -NH(wherein, R 6 and R 8 is as described above.) to react with an amine represented by the formula: [ka] (In the formula, R 4 ~R 6 and R 8 as defined above.) and Compound (31) and a compound of formula: [ka] (wherein n is an integer of 1 to 5) to form a compound represented by the formula: [ka] (In the formula, R 4 ~R 6 , R 8 , M and n are as defined above.

[0208] In the step (51), the reaction ratio of compound (31) and the acid anhydride is preferably 0.5 to 10 mol, more preferably 0.6 to 4.0 mol, still more preferably 1.2 to 4.0 mol, and particularly preferably 1.6 to 4.0 mol, relative to 1 mol of compound (31), in consideration of improving the yield and reducing waste.

[0209] The reaction in step (51) can be carried out in the presence of a base.

[0210] Examples of the base include amines, potassium hydroxide, sodium hydroxide, and potassium carbonate.

[0211] Examples of the amine 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, with pyridine or triethylamine being preferred.

[0212] The reaction temperature in step (51) is preferably from -78 to 150°C, more preferably from 0 to 150°C, even more preferably from 0 to 100°C, and particularly preferably from 20 to 80°C.

[0213] The reaction pressure in the step (51) is preferably 0 to 5 MPa, more preferably 0.1 to 1 MPa.

[0214] The reaction time in the step (51) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0215] The surfactant (1) may also be a compound represented by the formula: R 6 -OH(in the formula, R 6is as described above.) is reacted with fumaric acid halide to give an alcohol represented by the formula: [ka] (In the formula, R 6 as described above.) and Compound (61) is reacted with a sulfonating agent such as sodium bisulfite to produce a compound of the formula: [ka] (In the formula, R 6 and X are as defined above.)

[0216] The fumaric acid halide used in step (61) includes fumaryl chloride, fumaryl fluoride, fumaryl bromide, etc.

[0217] In the step (61), the reaction ratio of the alcohol and the fumaric acid halide is preferably 0.1 to 10 mol, more preferably 0.1 to 2.0 mol, still more preferably 0.1 to 2.0 mol, and particularly preferably 0.2 to 0.7 mol, relative to 1 mol of the alcohol, in consideration of improving yield and reducing waste.

[0218] The reaction in step (61) can be carried out in a solvent, such as an ester, a ketone, an aromatic hydrocarbon, an ether, a nitrogen-containing polar organic compound, a halogenated hydrocarbon, a nitrile, pyridine, or a mixture thereof.

[0219] 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.

[0220] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0221] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0222] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0223] 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.

[0224] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0225] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0226] The reaction temperature in step (61) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0227] The reaction pressure in the step (61) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0228] The reaction time in the step (61) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0229] In step (62), compound (62) is produced by addition reaction of compound (61) having a double bond with a sulfonating agent such as sodium hydrogen sulfite.

[0230] In the step (62), the reaction ratio of compound (61) and the sulfonating agent is preferably 0.5 to 20.0 mol, more preferably 0.6 to 10.0 mol, still more preferably 0.8 to 10.0 mol, and particularly preferably 1.2 to 10.0 mol, relative to 1 mol of compound (61), in consideration of improving the yield and reducing waste.

[0231] Step (62) can be carried out in a solvent, preferably a water-soluble solvent, such as water, alcohol, ether, or nitrile.

[0232] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0233] Examples of the ether include tetrahydrofuran, dioxane, and diethylene glycol diethyl ether.

[0234] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0235] The reaction temperature in step (62) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0236] The reaction pressure in step (62) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0237] The reaction time in step (62) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0238] The surfactant (1) may also be represented by the formula: [ka] (In the formula, R 10 , R 11 and Y are as defined above.) is sulfated to obtain a compound (70) represented by the formula: [ka] (In the formula, R 10 , R 11 and Y are as above. 100 is —OH or —OSO3M, where M is as defined above.

[0239] The sulfation in step (71) can be carried out by reacting compound (70) 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 (70). By adjusting the amount of the sulfating reagent used, one or both of the two -OH groups in compound (20) can be sulfated.

[0240] The sulfonation in step (71) can be carried out in a solvent, preferably an organic solvent, such as ether, halogenated hydrocarbon, aromatic hydrocarbon, pyridine, dimethyl sulfoxide, sulfolane, or nitrile.

[0241] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0242] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0243] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0244] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0245] The temperature for sulfonation in the step (71) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0246] The pressure for sulfonation in the step (71) is preferably 0 to 10 MPa, more preferably 0.1 to 5 MPa.

[0247] The time for sulfate esterification in the step (71) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0248] Compound (70) can also be represented by the formula: [ka] (In the formula, R 10 and Y are as above. 100 is an alkyl group.) is hydroxylated to give a compound (100) of the formula: [ka] (In the formula, R 10 , R100 and Y are as defined above.), and It can be produced by a production method including a step (102) of oxidizing compound (101) to obtain compound (70).

[0249] R 100 The alkyl group as R 100 -CH2- as the above-mentioned R 11 Configure.

[0250] The hydroxylation in step (101) can be carried out, for example, by (1) reacting compound (100) with phthalocyanine iron(II) (Fe(Pc)) and sodium borohydride in an oxygen atmosphere, or (2) reacting compound (100) with isopinocampheylborane (IpcBH) and then oxidizing the resulting intermediate (dialkylborane).

[0251] 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 (100).

[0252] In the method (1), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (100).

[0253] 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.

[0254] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0255] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0256] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0257] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0258] 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.

[0259] The reaction temperature in the method (1) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0260] The reaction pressure in the method (1) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0261] The reaction time in the method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0262] In the method (2), isopinocampheylborane can be used in an amount of 0.1 to 10.0 moles per mole of compound (100).

[0263] The reaction of compound (100) with isopinocampheylborane can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0264] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0265] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0266] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0267] The temperature for the reaction of compound (100) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0268] The pressure for the reaction of compound (100) with isopinocampheylborane is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0269] The reaction time of compound (100) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0270] 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.

[0271] The oxidation in method (2) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0272] The oxidation temperature in the method (2) is preferably from -78 to 150°C, more preferably from 0 to 100°C, and even more preferably from 10 to 80°C.

[0273] The oxidation pressure in the method (2) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0274] The oxidation time in method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0275] In step (102), examples of methods for oxidizing compound (101) include (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation), (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation), (c) a method using pyridinium chlorochromate (PCC), (d) a method using a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as NiCl2, and (e) a method using a hydrogen acceptor such as an aldehyde or ketone in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0276] The oxidation in step (102) can be carried out in a solvent, preferably water or an organic solvent, such as water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

[0277] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0278] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0279] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0280] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0281] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0282] The oxidation temperature in step (102) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0283] The oxidation pressure in the step (102) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0284] The oxidation time in step (102) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0285] Compound (70) can also be represented by the formula: [ka] (In the formula, R 10 , R 11 and Y are as above. 101 is an organic group.) to obtain compound (70).

[0286] R 101 is preferably an alkyl group having 1 to 20 carbon atoms. 101 may be the same or different.

[0287] The ozonolysis in step (201) can be carried out by reacting compound (200) with ozone, followed by post-treatment with a reducing agent.

[0288] Ozone can be generated by silent electrical discharge in oxygen gas.

[0289] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0290] The ozonolysis in step (201) 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.

[0291] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0292] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0293] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0294] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0295] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0296] The temperature for ozonolysis in the step (201) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0297] The pressure for ozonolysis in the step (201) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0298] The time for ozonolysis in the step (201) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0299] Compound (70) can also be represented by the formula: [ka] (In the formula, R 10 and Y are as above. 100 is an alkyl group.) is epoxidized to give a compound (300) represented by the formula: [ka] (In the formula, R 10 , R 100 and Y are as defined above.), Compound (301) and R 102 2CuLi(R 102 is an alkyl group) to form a dialkyl copper lithium compound represented by the formula: [ka] (In the formula, R 10 , R 100 , R 102 and Y are as defined above.), and It can be produced by a production method including a step (303) of oxidizing compound (302) to obtain compound (70).

[0300] R 100 and R 102 The alkyl group as R 100 R 102 -CH- as the above-mentioned R 11 Configure.

[0301] 2 R's 100 may be the same or different. 102 may be the same or different.

[0302] The epoxidation in step (301) can be carried out by reacting the compound (300) with an epoxidizing agent.

[0303] Examples of the epoxidizing agent include metachloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, peracids such as tert-butylhydroperoxode, 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 (300).

[0304] The epoxidation in step (301) 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.

[0305] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0306] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0307] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0308] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0309] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0310] 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.

[0311] The epoxidation temperature in the step (301) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0312] The pressure for epoxidation in the step (301) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0313] The epoxidation time in the step (301) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0314] In the step (302), the dialkyl copper lithium can be used in an amount of 0.5 to 10.0 moles per mole of the compound (301).

[0315] The reaction in step (302) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0316] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0317] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0318] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0319] The reaction temperature in step (302) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0320] The reaction pressure in step (302) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0321] The reaction time in step (302) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0322] In step (303), examples of methods for oxidizing compound (302) 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).

[0323] The oxidation in step (303) 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.

[0324] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0325] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0326] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0327] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0328] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0329] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0330] The oxidation temperature in step (303) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0331] The oxidation pressure in the step (303) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0332] The oxidation time in step (303) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0333] Compound (70) can also be represented by the formula: [ka] (In the formula, R 10 and Y are as above. 100 is an alkyl group.) to obtain compound (70).

[0334] The oxidation in step (401) can be carried out by reacting compound (400) with an oxidizing agent in the presence of water and a palladium compound.

[0335] Examples of the oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide, and copper trifluoromethanethiol; iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanethiol, and iron hexacyano; benzoquinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, and tetrachloro-1,4-benzoquinone; HO, MnO, KMnO, RuO, m-chloroperbenzoic acid, oxygen, and combinations thereof. 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 (400).

[0336] The amount of water used may be 0.5 to 1000 moles per mole of compound (400).

[0337] 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 (400).

[0338] The oxidation in step (401) 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.

[0339] 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.

[0340] 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.

[0341] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0342] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0343] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0344] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0345] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0346] 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.

[0347] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0348] The oxidation temperature in the step (401) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0349] The oxidation pressure in the step (401) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0350] The oxidation time in the step (401) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0351] Compound (100), compound (300) and compound (400) are represented by the formula: [ka] (In the formula, R 10 and Y are as above. 100 is an alkyl group. The compound can be produced by a production method including a step (501) of reacting an aldehyde represented by the formula (I) with a reducing agent to obtain compound (100).

[0352] In step (501), the aldehyde is dimerized by a reductive coupling reaction to produce compound (100), compound (300), and compound (400). Examples of reducing agents used in step (501) include samarium diiodide, titanium dichloride, vanadium trichloride, titanium tetrachloride, bis(cyclooctadiene)nickel, copper, magnesium, zinc, sodium, cerium trichloride, chromium oxide, and triphenyltin hydride. The reducing agents may be used in combination. The amount of the reducing agent used is preferably 0.001 to 10 mol, more preferably 0.01 to 5 mol, and even more preferably 0.1 to 2 mol, per mol of the aldehyde.

[0353] The reaction in step (501) can be carried out in a solvent, preferably an organic solvent, more preferably an ether, a halogenated hydrocarbon, pyridine, a nitrile, an aromatic hydrocarbon, or the like.

[0354] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0355] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0356] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

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

[0358] The reaction in step (501) is preferably carried out in the presence of an alcohol, such as methanol, ethanol, or isopropanol.

[0359] The reaction temperature in the step (501) is preferably from -78 to 200°C, more preferably from -20 to 100°C.

[0360] The reaction pressure in the step (501) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0361] The reaction time in the step (501) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0362] 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, when the obtained compound is a compound in which M is H, such as —COOH, —SO3H, or —OSO3H, these groups can be converted into salt forms by contacting with an alkali such as sodium carbonate or ammonia.

[0363] The hydrocarbon surfactant also includes a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). Furthermore, hydrocarbon surfactants obtained by subjecting the above hydrocarbon surfactants having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) to radical treatment or oxidation treatment can also be used. The radical treatment may be any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). For example, it involves adding deionized water and a hydrocarbon surfactant to a reactor, sealing the reactor, replacing the atmosphere with nitrogen, and then heating and pressurizing the reactor. Then, a polymerization initiator is added, the mixture is stirred for a certain period of time, and the pressure in the reactor is reduced to atmospheric pressure, followed by cooling. The oxidation treatment involves adding an oxidizing agent to a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). Examples of oxidizing agents include oxygen, ozone, hydrogen peroxide, manganese(IV) oxide, potassium permanganate, potassium dichromate, nitric acid, and sulfur dioxide.

[0364] The hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) may be a surfactant represented by the formula: RX (wherein R is a fluorine-free organic group having 1 to 2000 carbon atoms and having 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 1aR 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 3a Any two of these may be bonded to each other to form a ring.) A surfactant (a) represented by the following formula (b): [ka] (In the formula, R 1b R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2b and R 4b are independently H or a substituent. 3b is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. X b is H, metal atom, NR 5b 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 5b are H or organic groups, and may be the same or different. 1b , R 2b , R3b and R 4b Any two of may be bonded to each other to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6b represents H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents -OSO3X in the formula. b (b) a surfactant represented by the following formula (c): [ka] (In the formula, R 1c R is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond, and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2c and R 3c R is independently a single bond or a divalent linking group. 1c , R 2c and R 3c A has a total of 5 or more carbon atoms. c -COOX c or -SO3X c (X c is H, metal atom, NR 4c 4. An optionally substituted imidazolium, an optionally substituted pyridinium, or an optionally substituted phosphonium, wherein R 4c are H or organic groups, and may be the same or different. 1c , R 2c and R 3cAny two of these may be bonded to each other to form a ring.) and a surfactant (c) represented by the following formula (d): [ka] (In the formula, R 1d R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, and when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. 2d and R 4d are independently H or a substituent. 3d is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. A d -SO3X d or -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. 1d , R 2d , R 3d and R 4d Any two of may be bonded to each other to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents A in the formula. d It is more preferable that the surfactant (d) is at least one selected from the group consisting of surfactants (d) represented by the formula:

[0365] The surfactant (a) will now be described.

[0366] In formula (a), R 1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms. When the alkyl group has three or more carbon atoms, it may contain a carbonyl group (-C(=O)-) between two carbon atoms. When the alkyl group has two or more carbon atoms, it may also contain the carbonyl group at the terminal of the alkyl group. In other words, acyl groups such as an acetyl group represented by CH3-C(=O)- are also included in the alkyl group. Furthermore, when the alkyl group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, such as a furan ring. 1a In the above, a divalent heterocycle may be inserted between two carbon atoms, a divalent heterocycle may be located at a terminal and bonded to -C(=O)-, or a monovalent heterocycle may be located at the terminal of the alkyl group.

[0367] 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.

[0368] 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.

[0369] 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.

[0370] 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.

[0371] R 1a , R 2a and R 3ahas 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.

[0372] 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 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. The metal atom includes monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K, or Li. X 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.

[0373] 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.

[0374] Also, R 1a As the formula: [ka] (In the formula, n 11a is an integer between 0 and 10, and R 11a is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R 12a is an alkylene group having 0 to 3 carbon atoms. 11a is an integer between 2 and 10, R 12a may be the same or different. ) is more preferred.

[0375] n 11a is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably an integer of 1 to 3.

[0376] 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.

[0377] R 12ais 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.

[0378] 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-).

[0379] Examples of surfactant (a) include the following surfactants: a is as described above.

[0380] [ka]

[0381] [ka]

[0382] [ka]

[0383] [ka]

[0384] [ka]

[0385] [ka]

[0386] [ka]

[0387] [ka]

[0388] The surfactant (a) is a novel compound and can be produced, for example, by the production method exemplified below.

[0389] 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 201aare 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 Xa 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.

[0390] 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.

[0391] 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).

[0392] 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.

[0393] R 21a is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0394] Examples of the chlorosilane compound include: [ka] Examples include:

[0395] 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.

[0396] 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.

[0397] 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.

[0398] 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.

[0399] 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.

[0400] The reaction in step (12a) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0401] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

[0402] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0403] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0404] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0405] 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.

[0406] The reaction temperature in step (12a) is preferably 40 to 60°C, more preferably 50 to 55°C.

[0407] The reaction pressure in step (12a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0408] The reaction time in step (12a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0409] 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).

[0410] 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.

[0411] 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.

[0412] The reaction temperature in step (13a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0413] The reaction pressure in step (13a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0414] The reaction time in step (13a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0415] 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.

[0416] 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.

[0417] 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.

[0418] 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.

[0419] 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.

[0420] 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.

[0421] The reaction temperature in step (14a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0422] The reaction pressure in step (14a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0423] The reaction time in step (14a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0424] 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.

[0425] 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.

[0426] 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, Ea 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 , R 24a 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.)

[0427] R 1aWhen 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.

[0428] 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.

[0429] 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.

[0430] The reaction in step (21a) can be carried out in a solvent in the presence of a base.

[0431] Examples of the base include sodium amide, sodium hydride, sodium methoxide, and sodium ethoxide.

[0432] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0433] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0434] 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.

[0435] The reaction temperature in step (21a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0436] The reaction pressure in the step (21a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0437] The reaction time in step (21a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0438] 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).

[0439] 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.

[0440] 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.

[0441] The reaction temperature in step (22a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0442] The reaction pressure in the step (22a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0443] The reaction time in step (22a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0444] 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.

[0445] 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.

[0446] 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.

[0447] 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.

[0448] 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.

[0449] 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.

[0450] The reaction temperature in step (23a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0451] The reaction pressure in the step (23a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0452] The reaction time in step (23a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0453] 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.

[0454] 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.

[0455] 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 a is 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.

[0456] 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.

[0457] 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.

[0458] 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.

[0459] The reaction in step (31a) can be carried out in a solvent, preferably hexane.

[0460] The reaction temperature in step (31a) is preferably from -100 to -40°C, more preferably from -80 to -50°C.

[0461] The reaction pressure in the step (31a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0462] The reaction time in step (31a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0463] 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.

[0464] 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.

[0465] The reaction temperature in step (32a) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0466] The reaction pressure in step (32a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0467] The reaction time in step (32a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0468] 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).

[0469] 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.

[0470] 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.

[0471] The reaction temperature in step (33a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0472] The reaction pressure in the step (33a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0473] The reaction time in step (33a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0474] 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.

[0475] 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.

[0476] 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.

[0477] 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.

[0478] 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.

[0479] 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.

[0480] The reaction temperature in step (34a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0481] The reaction pressure in the step (34a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0482] The reaction time in step (34a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0483] 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.

[0484] 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.

[0485] The surfactant (a) may also be a compound represented by the formula: [ka] (In the formula, R 1a As mentioned above, R 21ais 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.)

[0486] 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.

[0487] R 21a is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0488] 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.

[0489] The reaction in step (41a) is preferably carried out in the presence of a metal catalyst, such as ruthenium.

[0490] 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.

[0491] The reaction in step (41a) can be carried out in a polar solvent, preferably water, acetonitrile, dimethylacetamide, or dimethylformamide.

[0492] The reaction temperature in step (41a) is preferably 20 to 160°C, more preferably 40 to 140°C.

[0493] The reaction pressure in the step (41a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0494] The reaction time in step (41a) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0495] 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.

[0496] 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.

[0497] 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.

[0498] 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.

[0499] 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.

[0500] 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.

[0501] The reaction temperature in step (42a) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0502] The reaction pressure in the step (42a) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0503] The reaction time in step (42a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

[0504] 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.

[0505] 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.

[0506] Next, the surfactant (b) will be described.

[0507] In formula (b), R 1b 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. 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.

[0508] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0509] R 1bThe 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.

[0510] 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.

[0511] R 1b 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.

[0512] In formula (b), R 2b and R 4b are independently H or a substituent. 2b and R 4b may be the same or different.

[0513] R 2b and R 4bThe 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.

[0514] 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.

[0515] R 2b and R 4b 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).

[0516] 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.

[0517] In formula (b), R 3b R is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3bWhen there are a plurality of, they may be the same or different.

[0518] 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.

[0519] 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-).

[0520] 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.

[0521] 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.

[0522] 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.

[0523] 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.

[0524] 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 5b is H or an organic group. 5b may be the same or different. 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. 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. 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.

[0525] In formula (b), L represents a single bond, -CO2-B-*, -OCO-B-*, or -CONR6b -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

[0526] L is preferably a single bond.

[0527] 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.

[0528] 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.

[0529] 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.

[0530] In the surfactant (b), the integral value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and even more preferably 70 or less.

[0531] The above integral value is measured at room temperature in a heavy water solvent. The heavy water is set to 4.79 ppm.

[0532] Examples of the surfactant (b) include, for example, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2CH2OSO3Na, CH3C(O)CH2CH2CH2CH2OSO3Na, (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2OSO3Na, CH3CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2OSO3Na、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Liぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4、 CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH(CH3)2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2CH2CH2CH2OSO3Naぁ CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)CH2CH2CH2CH2OSO3Naぁ CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2OSO3Naぁ CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2CH2OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OSO3Na, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3H, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Li, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3K, CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3NH4, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3Na and the like can be mentioned.

[0533] Surfactant (b) is a novel compound and can be produced, for example, by the production methods exemplified below.

[0534] Surfactant (b) has 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 6b CO-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.

[0535] R 11b The alkyl group as above preferably does not contain a carbonyl group. R 11b 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.

[0536] 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.

[0537] 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).

[0538] 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).

[0539] In the method (1), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (10b).

[0540] 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.

[0541] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0542] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0543] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0544] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0545] 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.

[0546] The reaction temperature in the method (1) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0547] The reaction pressure in the method (1) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0548] The reaction time in the method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0549] In the method (2), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per mole of compound (10b).

[0550] 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.

[0551] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0552] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0553] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0554] The temperature for the reaction of compound (10b) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0555] 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.

[0556] The reaction time of compound (10b) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0557] 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.

[0558] The oxidation in method (2) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0559] The oxidation temperature in the method (2) is preferably 0 to 100°C, more preferably 0 to 80°C.

[0560] The oxidation pressure in the method (2) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0561] The oxidation time in method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0562] In step (12b), examples of methods for oxidizing compound (11b) include (a) a method using Jones reagent (CrO3 / H2SO4) (Jones oxidation), (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation), (c) a method using pyridinium chlorochromate (PCC), (d) a method using a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as NiCl2, and (e) a method using a hydrogen acceptor such as an aldehyde or ketone in the presence of an aluminum catalyst such as Al(CH3)3 or Al[OCH(CH3)2]3 (Oppenauer oxidation).

[0563] 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.

[0564] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0565] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0566] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0567] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0568] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0569] The oxidation temperature in step (12b) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0570] The oxidation pressure in the step (12b) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0571] The oxidation time in step (12b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0572] The sulfation in step (13b) can be carried out by reacting compound (12b) with a sulfating reagent. Examples of the sulfating reagent include sulfur trioxide amine complexes such as sulfur trioxide pyridine complex, sulfur trioxide trimethylamine complex, and sulfur trioxide triethylamine complex; sulfur trioxide amide complexes such as sulfur trioxide dimethylformamide complex; sulfuric acid-dicyclohexylcarbodiimide; chlorosulfuric acid; concentrated sulfuric acid; and sulfamic acid. The amount of the sulfating reagent used is preferably 0.5 to 10 mol, more preferably 0.5 to 5 mol, and even more preferably 0.7 to 4 mol, per 1 mol of compound (12b).

[0573] 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.

[0574] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0575] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0576] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0577] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0578] The temperature for sulfonation in step (13b) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0579] The pressure for sulfonation in step (13b) is preferably 0 to 10 MPa, more preferably 0.1 to 5 MPa.

[0580] The time for sulfate esterification in step (13b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0581] 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.

[0582] R 101b is preferably an alkyl group having 1 to 20 carbon atoms. 101b may be the same or different.

[0583] The ozonolysis in step (21b) can be carried out by reacting compound (20b) with ozone, followed by post-treatment with a reducing agent.

[0584] Ozone can be generated by silent electrical discharge in oxygen gas.

[0585] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0586] 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.

[0587] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0588] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0589] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0590] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0591] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0592] The temperature for ozonolysis in step (21b) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0593] The pressure for ozonolysis in the step (21b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0594] The time for ozonolysis in step (21b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0595] 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.

[0596] 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.

[0597] 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.

[0598] 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.

[0599] 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.

[0600] 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.

[0601] 2 R's 22b may be the same or different.

[0602] R 21b and R 22bPreferably, the total number of carbon atoms is 1 to 7, more preferably 1 or 2, and most preferably 1.

[0603] The epoxidation in step (31b) can be carried out by reacting compound (30b) with an epoxidizing agent.

[0604] 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).

[0605] 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.

[0606] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0607] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0608] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0609] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0610] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0611] 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.

[0612] The epoxidation temperature in step (31b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0613] The pressure for epoxidation in step (31b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0614] The epoxidation time in step (31b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0615] 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).

[0616] 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.

[0617] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0618] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0619] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0620] The reaction temperature in step (32b) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0621] The reaction pressure in step (32b) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0622] The reaction time in step (32b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0623] 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).

[0624] 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.

[0625] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0626] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0627] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0628] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0629] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0630] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0631] The oxidation temperature in the step (33b) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0632] The oxidation pressure in the step (33b) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0633] The oxidation time in step (33b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0634] 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.

[0635] 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 represented by 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.

[0636] 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.

[0637] 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).

[0638] The water can be used in an amount of 0.5 to 1000 moles per mole of compound (10b).

[0639] 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).

[0640] 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.

[0641] 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.

[0642] 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.

[0643] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0644] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0645] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0646] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0647] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0648] 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.

[0649] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0650] The oxidation temperature in step (41b) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

[0651] The oxidation pressure in the step (41b) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.

[0652] The oxidation time in step (41b) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0653] 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.

[0654] The surfactant (b) may also be a compound represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -OH (In the formula, R 2b , R 11b and n are as defined above.) is reacted with a halogenating agent to obtain a compound represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -Z 51b (In the formula, R 2b , R 11b and n is as above. Z 51b is a halogen atom), Compound (51) and HO-R 3b -L-OH(L, R 3b is as described above.) to react with an alkylene glycol represented by the following formula: R 11b -CH=CH-(CR 2b 2) n -OR 3b -L-OH (In the formula, L, R 2b , R 3b , R 11b and n is as defined above.), Compound (52) is oxidized to give the compound of the following formula: [ka] (In the formula, L, R2b , R 3b , R 11b and n is as defined above.), and The compound (53) is converted into a sulfate ester to obtain a compound of the following formula: [ka] (In the formula, L, R 2b , R 3b , R 11b , n and X b can be produced by a production method including a step (54) of obtaining a compound (54) represented by the formula:

[0655] Z 51b is preferably F, Cl, Br or I, and more preferably Br.

[0656] Examples of the halogenating agent used in step (51) include N-bromosuccinimide and N-chlorosuccinimide. The halogenating agent can be used in an amount of 0.5 to 10.0 mol per 1 mol of compound (50).

[0657] The reaction in step (51) can be carried out in the presence of a phosphine such as triphenylphosphine. The phosphines can be used in an amount of 0.5 to 10.0 moles per mole of compound (50).

[0658] The reaction in step (51) can be carried out in a solvent, preferably an organic solvent, such as an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0659] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0660] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0661] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0662] The reaction temperature in step (51) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0663] The reaction pressure in step (51) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0664] The reaction time in step (51) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0665] In the step (52), the alkylene glycol can be used in an amount of 0.5 to 10.0 moles per mole of the compound (51).

[0666] The reaction in step (52) can be carried out in the presence of a base, such as sodium hydride, sodium hydroxide, or potassium hydroxide. The base can be used in an amount of 0.5 to 10.0 moles per mole of compound (51).

[0667] The reaction in step (52) can be carried out in a solvent, preferably an organic solvent, such as a nitrogen-containing polar organic compound, an ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[0668] 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.

[0669] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0670] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0671] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0672] The reaction temperature in step (52) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

[0673] The reaction pressure in step (52) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0674] The reaction time in step (52) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0675] The oxidation in step (53) can be carried out by reacting compound (52) with an oxidizing agent in the presence of water and a palladium compound, and the same conditions as those for the oxidation in step (41) can be used.

[0676] The sulfate esterification in step (54) can be carried out by reacting compound (53) with a sulfating reagent, and the same conditions as those for the sulfate esterification in step (13) can be used.

[0677] 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.

[0678] Among the methods for producing the surfactant (b), a production method including the above steps (41b) and (42b) is preferred.

[0679] The surfactant (c) will now be explained.

[0680] 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.

[0681] 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.

[0682] 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.

[0683] 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.

[0684] 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.

[0685] 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.

[0686] 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. 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. The metal atom includes monovalent and divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K, or Li. X c H, alkali metals (group 1), alkaline earth metals (group 2) or NR 4c X is preferred, H, Na, K, Li or NH is more preferred because they are easily soluble in water, Na, K or NH is even more preferred because they are even more easily soluble in water, Na or NH is particularly preferred, and NH is most preferred because it is easily removed. c When is NH4, the surfactant has excellent solubility in an aqueous medium, and metal components are less likely to remain in the PTFE or the final product.

[0687] 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.

[0688] Also, R 1c As the formula: [ka] (In the formula, n 11c is an integer between 0 and 10, and R 11c is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R 12c is an alkylene group having 0 to 3 carbon atoms. 11c is an integer between 2 and 10, R 12c may be the same or different. ) is more preferred.

[0689] 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.

[0690] 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.

[0691] 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.

[0692] 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-).

[0693] Examples of the surfactant (c) include the following surfactants: c is as described above.

[0694] [ka]

[0695] [ka]

[0696] [ka]

[0697] [ka]

[0698] [ka]

[0699] [ka]

[0700] [ka]

[0701] [ka]

[0702] The surfactant (c) is a novel compound and can be produced, for example, by the production method exemplified below.

[0703] 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:

[0704] 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.

[0705] 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).

[0706] 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.

[0707] R 21c is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0708] Examples of the chlorosilane compound include: [ka] Examples include:

[0709] 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.

[0710] 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.

[0711] 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.

[0712] 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.

[0713] 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.

[0714] The reaction in step (12c) can be carried out in a solvent in the presence of a thiazolium salt and a base.

[0715] Examples of the thiazolium salt include 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

[0716] Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene, triethylamine, and the like.

[0717] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and even more preferably an alcohol or an ether.

[0718] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0719] 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.

[0720] The reaction temperature in step (12c) is preferably 40 to 60°C, more preferably 50 to 55°C.

[0721] The reaction pressure in step (12c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0722] The reaction time in step (12c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0723] 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).

[0724] 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.

[0725] 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.

[0726] The reaction temperature in step (13c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0727] The reaction pressure in step (13c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0728] The reaction time in step (13c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0729] The oxidation in step (14c) can be carried out in a solvent in the presence of sodium chlorite.

[0730] 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.

[0731] 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.

[0732] 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.

[0733] 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:

[0734] 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.

[0735] 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.

[0736] 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.

[0737] The reaction in step (21c) can be carried out in a solvent in the presence of a base.

[0738] Examples of the base include sodium amide, sodium hydride, sodium methoxide, and sodium ethoxide.

[0739] The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

[0740] Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

[0741] 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.

[0742] The reaction temperature in step (21c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0743] The reaction pressure in the step (21c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0744] The reaction time in step (21c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0745] 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).

[0746] 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.

[0747] 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.

[0748] The reaction temperature in step (22c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0749] The reaction pressure in step (22c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0750] The reaction time in step (22c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0751] The oxidation in step (23c) can be carried out in a solvent in the presence of sodium chlorite.

[0752] The solvent may be alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0753] 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.

[0754] 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.

[0755] 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:

[0756] 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.

[0757] 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.

[0758] 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.

[0759] The reaction in step (31c) can be carried out in a solvent, preferably hexane.

[0760] The reaction temperature in step (31c) is preferably from -100 to -40°C, more preferably from -80 to -50°C.

[0761] The reaction pressure in the step (31c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0762] The reaction time in step (31c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

[0763] 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.

[0764] 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.

[0765] The reaction temperature in step (32c) is preferably 30 to 100°C, more preferably 40 to 90°C.

[0766] The reaction pressure in step (32c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0767] The reaction time in step (32c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0768] The elimination reaction of the leaving group in step (33c) can be carried out using fluoride ions or an acid. Examples of methods for eliminating the leaving group include a method using hydrofluoric acid, a method using an amine complex of hydrogen fluoride such as pyridine·nHF or triethylamine·nHF, a method using an inorganic salt such as cesium fluoride, potassium fluoride, lithium borofluoromethane (LiBF4), or ammonium fluoride, and a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

[0769] 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.

[0770] 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.

[0771] The reaction temperature in step (33c) is preferably 0 to 40°C, more preferably 0 to 20°C.

[0772] The reaction pressure in the step (33c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0773] The reaction time in step (33c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

[0774] The oxidation in step (34c) can be carried out in a solvent in the presence of sodium chlorite.

[0775] The solvent may be alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0776] 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.

[0777] After completion of each step, the purity of the resulting compound may be increased by removing the solvent, or by carrying out distillation, purification, or the like.

[0778] 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:

[0779] 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.

[0780] 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.

[0781] 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.

[0782] The reaction in step (51c) can be carried out in a polar solvent, preferably water or acetonitrile.

[0783] The reaction temperature in step (51c) is preferably 20 to 100°C, more preferably 40 to 100°C.

[0784] The reaction pressure in the step (51c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0785] The reaction time in step (51c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0786] 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.

[0787] 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.

[0788] 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.

[0789] The reaction in step (52c) can be carried out in a polar solvent, preferably water.

[0790] The reaction temperature in step (52c) is preferably 20 to 100°C, more preferably 40 to 100°C.

[0791] The reaction pressure in the step (52c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0792] The reaction time in step (52c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0793] In step (53c), compound (52c) is heated in the presence of an acid to open the furan ring.

[0794] The acid is preferably hydrochloric acid or sulfuric acid.

[0795] The reaction in step (53c) can be carried out in a polar solvent, preferably water.

[0796] The reaction temperature in step (53c) is preferably 50 to 100°C, more preferably 70 to 100°C.

[0797] The reaction pressure in the step (53c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0798] The reaction time in step (53c) is preferably 0.1 to 72 hours, more preferably 1 to 12 hours.

[0799] The oxidation in step (54c) can be carried out in a solvent in the presence of sodium chlorite.

[0800] The solvent may be tert-butyl alcohol or water, and a disodium hydrogen phosphate solution may be used as a buffer solution.

[0801] 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.

[0802] 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.

[0803] 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:

[0804] 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.

[0805] R 21c is preferably a single bond or a linear or branched alkylene group having one or more carbon atoms.

[0806] 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.

[0807] The reaction in step (61c) is preferably carried out in the presence of a metal catalyst, such as ruthenium.

[0808] 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.

[0809] The reaction in step (61c) can be carried out in a polar solvent, preferably water, acetonitrile, dimethylacetamide, or dimethylformamide.

[0810] The reaction temperature in step (61c) is preferably 20 to 160°C, more preferably 40 to 140°C.

[0811] The reaction pressure in the step (61c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0812] The reaction time in step (61c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0813] 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.

[0814] 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.

[0815] The reaction in step (62c) can be carried out in a polar solvent, preferably water.

[0816] The reaction temperature in step (62c) is preferably 0 to 100°C, more preferably 20 to 100°C.

[0817] The reaction pressure in the step (62c) is preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.

[0818] The reaction time in step (62c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

[0819] 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.

[0820] 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.

[0821] The surfactant (d) will now be described.

[0822] 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.

[0823] In this specification, the "number of carbon atoms" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

[0824] 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.

[0825] 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.

[0826] 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.

[0827] In formula (d), R 2d and R 4d are independently H or a substituent. 2d and R 4d may be the same or different.

[0828] 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.

[0829] 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.

[0830] 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).

[0831] 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.

[0832] 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.

[0833] 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.

[0834] 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-).

[0835] R 1d , R 2d , R 3d and R 4d Any two of these may be bonded to each other to form a ring.

[0836] 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.

[0837] 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.

[0838] 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.

[0839] 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 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. 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. 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.

[0840] 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

[0841] L is preferably a single bond.

[0842] 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.

[0843] 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.

[0844] 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.

[0845] The above integral value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

[0846] 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ぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ (CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ (CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ (CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2CH2SO3Naぁ CH3C(O)CH2CH2SO3Naぁ CH3C(O)CH2SO3Naぁ CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Naぁ 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.

[0847] The surfactant (d) is a novel compound and can be produced, for example, by the production method exemplified below.

[0848] 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:

[0849] 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).

[0850] 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.

[0851] The reaction temperature in step (11d) is preferably from -78 to 150°C, more preferably from -20 to 100°C.

[0852] The reaction pressure in the step (11d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0853] The reaction time in step (11d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0854] 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:

[0855] The oxidation in step (21d) can be carried out by reacting compound (20d) with a nitrosating agent.

[0856] As the nitrosating agent, sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite, etc. can be used.

[0857] The nitrosating agent can be used in an amount of 0.5 to 10 moles per mole of compound (20d).

[0858] The oxidation in step (21d) can be carried out in a solvent, such as trifluoroacetic acid or acetonitrile.

[0859] The oxidation temperature in step (21d) is preferably from -78 to 200°C, more preferably from -20 to 100°C.

[0860] The oxidation pressure in the step (21d) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.

[0861] The oxidation time in step (21d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 24 hours.

[0862] 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, L, p, and q are as defined above. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-* or -CO- (However, -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d The carbonyl group contained in CO-B- is excluded.) B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6d is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * indicates the side bonded to -CH2- in the formula. ) is ). Compound (100d) represented by the following formula: [ka] (In the formula, R 11d and Y 1dis as described above.), and Compound (101d) is oxidized to give a compound of the following formula: [ka] (In the formula, R 11d and Y 1d can be produced by a production method including a step (102d) of obtaining a compound (102d) represented by the formula (102d) as described above.

[0863] 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.

[0864] 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.

[0865] 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).

[0866] 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).

[0867] In the method (1d), sodium borohydride can be used in an amount of 0.5 to 20 moles per mole of compound (100d).

[0868] 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.

[0869] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0870] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0871] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0872] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0873] 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.

[0874] The reaction temperature in the method (1d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0875] The reaction pressure in the method (1d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0876] The reaction time in the method (1d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0877] In the method (2d), isopinocampheylborane can be used in an amount of 1.0 to 10.0 moles per mole of compound (100d).

[0878] 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.

[0879] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0880] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0881] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0882] The temperature for the reaction of compound (100d) with isopinocampheylborane is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0883] 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.

[0884] The reaction time of compound (100d) with isopinocampheylborane is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0885] 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.

[0886] The oxidation in the method (2d) can be carried out in a solvent, such as water, methanol, or ethanol, with water being preferred.

[0887] The oxidation temperature in the method (2d) is preferably 0 to 100°C, more preferably 0 to 80°C.

[0888] The oxidation pressure in the method (2d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0889] The oxidation time in the method (2d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0890] 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).

[0891] 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.

[0892] Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, with acetone being preferred.

[0893] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0894] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0895] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0896] Examples of the nitrile include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile, and among these, acetonitrile is preferred.

[0897] The oxidation temperature in step (102d) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0898] The oxidation pressure in the step (102d) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.

[0899] The oxidation time in step (102d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.

[0900] 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.

[0901] R 101d is preferably an alkyl group having 1 to 20 carbon atoms. 101d may be the same or different.

[0902] The ozonolysis in step (201d) can be carried out by reacting compound (200d) with ozone, followed by post-treatment with a reducing agent.

[0903] Ozone can be generated by silent electrical discharge in oxygen gas.

[0904] Examples of reducing agents used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, with phosphines being preferred.

[0905] 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.

[0906] Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, etc. Among these, methanol and ethanol are preferred.

[0907] Examples of the carboxylic acids include acetic acid, propionic acid, etc. Among these, acetic acid is preferred.

[0908] Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, and among these, diethyl ether and tetrahydrofuran are preferred.

[0909] Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, with dichloromethane and chloroform being preferred.

[0910] Examples of the aromatic hydrocarbon include benzene, toluene, and xylene, with benzene and toluene being preferred.

[0911] The temperature for ozonolysis in the step (201d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

[0912] The pressure for ozonolysis in the step (201d) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0913] The time for ozonolysis in the step (201d) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.

[0914] 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.

[0915] 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.

[0916] 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 contai...

Claims

1. A method for producing a purified aqueous polytetrafluoroethylene dispersion, comprising a step of removing or reducing a compound represented by the following general formula (1) from an aqueous polytetrafluoroethylene dispersion obtained by a production method including a step of emulsion polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, wherein the aqueous polytetrafluoroethylene dispersion contains modified polytetrafluoroethylene comprising tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, and the content of the modified monomer units is in the range of 0.0001 to 2 mol%: General formula (1): (H-(CF 2 ) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

2. A method for producing a purified aqueous polytetrafluoroethylene dispersion according to claim 1, wherein the step of removing or reducing the compound represented by general formula (1) includes a step of subjecting the aqueous polytetrafluoroethylene dispersion to an ion exchange treatment and / or concentration treatment.

3. A method for producing polytetrafluoroethylene powder, comprising the steps of: emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant; and removing or reducing a compound represented by the following general formula (1) from the polytetrafluoroethylene powder obtained by the method, the step of removing or reducing the compound represented by general formula (1) includes a step of heat-treating the polytetrafluoroethylene powder at a temperature of 200°C or higher, The polytetrafluoroethylene powder is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, and the content of the modified monomer units is in the range of 0.0001 to 2 mol%. A method for producing a modified polytetrafluoroethylene powder, comprising: General formula (1): (H-(CF 2 ) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

4. A method for producing a molded article using polytetrafluoroethylene produced by a production method including a step of emulsion polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, comprising: The method includes a step of removing or reducing a compound represented by the following general formula (1): the step of removing or reducing the compound represented by general formula (1) includes a step of heat treatment at a temperature of 200° C. or higher, The polytetrafluoroethylene powder contains modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, and the content of the modified monomer units is in the range of 0.0001 to 2 mol%. A method for producing a polytetrafluoroethylene molded article, comprising: General formula (1): (H-(CF 2 ) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

5. A method for producing polytetrafluoroethylene, the method comprising the step of emulsion-polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, and the step of contacting the polytetrafluoroethylene with a fluorine radical source at a temperature above 100°C to remove or reduce the compound represented by the following general formula (1): The polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, and the content of the modified monomer units is in the range of 0.0001 to 2 mol%. A method for producing modified polytetrafluoroethylene, comprising: General formula (1): (H-(CF 2 ) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

6. A method for producing polytetrafluoroethylene, the method comprising the step of emulsion polymerizing tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant, and the step of contacting the polytetrafluoroethylene with a fluorine radical source to remove or reduce a compound represented by the following general formula (1), wherein the amount of the fluorine radical source added is 0.5 parts by weight or more per 100 parts by weight of polytetrafluoroethylene, calculated as fluorine atoms: The polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, and the content of the modified monomer units is in the range of 0.0001 to 2 mol%. A method for producing polytetrafluoroethylene, comprising: General formula (1): (H-(CF 2 ) m -COO) p M 1 (In the formula, m is 3 to 19, M 1 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

7. A polymer comprising polytetrafluoroethylene, the polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, the content of the modified monomer units being in the range of 0.0001 to 2 mol %, The content of the compound represented by the following general formula (3) is 1000 ppb or less relative to polytetrafluoroethylene, A composition containing a compound represented by the following general formula (5) in an amount of 1000 ppb or less relative to polytetrafluoroethylene, and a nonionic surfactant in an amount of 1% or more per polytetrafluoroethylene: General formula (3): (H-(CF 2 ) 8 -SO 3 ) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and q is 1 or 2.) General formula (5): (H-(CF 2 ) 13 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

8. A polymer comprising polytetrafluoroethylene, the polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, the content of the modified monomer units being in the range of 0.0001 to 2 mol %, The content of the compound represented by the following general formula (3) is 1000 ppb or less relative to polytetrafluoroethylene, The compound includes at least one of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'): The content of the compound represented by the following general formula (5) is 1000 ppb or less relative to polytetrafluoroethylene, A composition containing a compound represented by the following general formula (5') in an amount of 1000 ppb or less relative to polytetrafluoroethylene, and containing a nonionic surfactant in an amount of 1% or more per polytetrafluoroethylene. General formula (3): (H-(CF 2 ) 8 -SO 3 ) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and q is 1 or 2.) General formula (5): (H-(CF 2 ) 13 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.) General formula (5'): (H-(CF 2 ) 14 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

9. The composition described in claim 7 or 8, which is an aqueous dispersion.

10. A polymer comprising polytetrafluoroethylene, the polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, the content of the modified monomer units being in the range of 0.0001 to 2 mol %, The content of the compound represented by the following general formula (3) is 1000 ppb or less relative to polytetrafluoroethylene, A composition containing a compound represented by the following general formula (5) in an amount of 1000 ppb or less relative to polytetrafluoroethylene: General formula (3): (H-(CF 2 ) 8 -SO 3 ) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and q is 1 or 2.) General formula (5): (H-(CF 2 ) 13 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

11. A polymer comprising polytetrafluoroethylene, the polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, the content of the modified monomer units being in the range of 0.0001 to 2 mol %, The content of the compound represented by the following general formula (3) is 1000 ppb or less relative to polytetrafluoroethylene, The compound includes at least one of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'): The content of the compound represented by the following general formula (5) is 1000 ppb or less relative to polytetrafluoroethylene, A composition having a content of a compound represented by the following general formula (5') of 1000 ppb or less relative to polytetrafluoroethylene: General formula (3): (H-(CF 2 ) 8 -SO 3 ) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and q is 1 or 2.) General formula (5): (H-(CF 2 ) 13 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.) General formula (5'): (H-(CF 2 ) 14 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

12. A polymer comprising polytetrafluoroethylene, the polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, the content of the modified monomer units being in the range of 0.0001 to 2 mol %, The content of the compound represented by the following general formula (3) is 1000 ppb or less relative to polytetrafluoroethylene, A composition containing a compound represented by the following general formula (5) in an amount of 25 ppb or less relative to polytetrafluoroethylene: General formula (3): (H-(CF 2 ) 8 -SO 3 ) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and q is 1 or 2.) General formula (5): (H-(CF 2 ) 13 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

13. A polymer comprising polytetrafluoroethylene, the polytetrafluoroethylene is a modified polytetrafluoroethylene containing tetrafluoroethylene units and modified monomer units based on a modified monomer copolymerizable with tetrafluoroethylene, the content of the modified monomer units being in the range of 0.0001 to 2 mol %, The content of the compound represented by the following general formula (3) is 1000 ppb or less relative to polytetrafluoroethylene, The compound includes at least one of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'): The content of the compound represented by the following general formula (5) is 25 ppb or less relative to polytetrafluoroethylene, A composition having a content of a compound represented by the following general formula (5') of 25 ppb or less relative to polytetrafluoroethylene: General formula (3): (H-(CF 2 ) 8 -SO 3 ) q M 2 (In the formula, M 2 is H, a metal atom, NR 5 4 (R 5 may be the same or different and is H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and q is 1 or 2.) General formula (5): (H-(CF 2 ) 13 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.) General formula (5'): (H-(CF 2 ) 14 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.)

14. The composition according to any one of claims 10 to 13, further comprising a compound represented by the following general formula (7) in an amount of 1000 ppb or less relative to polytetrafluoroethylene: General formula (7): (F-(CF 2 ) 7 -COO) p M 1 (In the formula, M 1 represents H, a metal atom, NR 5 4 (R 5 may be the same or different and represents H or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent; and p is 1 or 2.) 15. The composition according to claim 7, wherein the content of the compound represented by general formula (3) is 25 ppb or less relative to polytetrafluoroethylene.

16. A composition described in any one of claims 7 to 15, wherein the polytetrafluoroethylene is obtained by polymerization using an anionic hydrocarbon surfactant.

17. A composition described in any one of claims 10 to 16, which is a powder.

18. A molded body comprising the composition of claim 17.

19. The molded body according to claim 18, which is an elongated body.