Methods for producing refined polytetrafluoroethylene powder, methods for producing polytetrafluoroethylene molded bodies, polytetrafluoroethylene-containing components, and molded bodies containing this component.

Abstract

The invention relates to a method for producing refined polytetrafluoroethylene powder, which includes the step of removing or reducing the compound expressed by the following formula (1): Formula (1): (H-(CF2)m-COO)pM1. The invention also relates to a method for producing polytetrafluoroethylene molded bodies, polytetrafluoroethylene-containing components and molded bodies containing such components.

Description

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

[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.

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

[0003] Special Publication No. 2013-542309

[0004] It has been found that the production of polytetrafluoroethylene using a hydrocarbon surfactant results in the production of specific fluorine-containing compounds. An object of the present invention is to obtain an aqueous polytetrafluoroethylene dispersion and polytetrafluoroethylene powder from which the fluorine-containing compounds have been removed or reduced. Another object of the present invention is to produce a polytetrafluoroethylene molded article from which the 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 fluorine-containing compounds have been removed or reduced.

[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. ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. q is 1 or 2. The step of removing or reducing the compound represented by general formula (1) or (2) above preferably includes a step of subjecting the polytetrafluoroethylene aqueous 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-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) ｑ M ２ (wherein n is 4 to 20. M ２ is H, metal atom, NR ５４ (R ５ may be the same or different and are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. q is 1 or 2. The step of removing or reducing the compound represented by general formula (1) or (2) above preferably includes a step of heat-treating the polytetrafluoroethylene powder obtained using the hydrocarbon surfactant at a temperature of 160°C or higher.

[0007] The present invention further relates to a method for producing a molded article using polytetrafluoroethylene produced using a hydrocarbon surfactant, the method comprising the step of removing or reducing the amount of a compound represented by the following general formula (1) or (2): General formula (1): (H-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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 general formula (1) or (2) above preferably includes a step of heat treatment at a temperature of 160°C or higher.

[0008] The present invention also provides 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-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), 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.

[0009] The present invention also relates to a method for producing polytetrafluoroethylene, which comprises a 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), and 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. ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a metal atom, NR ５４ (R ５ may be the same or different and are 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. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), 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.

[0010] The present invention also provides a composition containing polytetrafluoroethylene and substantially free of a compound represented by the following general formula (3): (H—(CF ２ ) ８ -SO ３ ) ｑ M ２ (In the formula, 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 content of the compound represented by the above general formula (3) is preferably 1000 ppb or less, and more preferably 25 ppb or less, relative to polytetrafluoroethylene.

[0011] One aspect of the present invention is a composition containing a compound represented by the following general formula (4) in an amount of 1000 ppb or less relative to polytetrafluoroethylene, and a nonionic surfactant in an amount of 1% or more per polytetrafluoroethylene. 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 are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. 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 the content of a nonionic surfactant is 1% / polytetrafluoroethylene or more. General formula (4'): (H-(CF ２ ) ８ -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 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) in an amount of 1000 ppb or less relative to polytetrafluoroethylene, and containing a nonionic surfactant in an amount of 1% / polytetrafluoroethylene or more. 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 ５may be the same or different, and are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. 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 the content of a nonionic surfactant is 1% / polytetrafluoroethylene or more. 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 are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. p is 1 or 2.) One aspect of these present 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. Also, 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 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. Another aspect of the present invention is 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 the 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 are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. p is 1 or 2.) One aspect of these present 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.

[0015] The method for producing a purified polytetrafluoroethylene aqueous dispersion of the present invention can remove or reduce the compound represented by general formula (1) or (2) present in the resulting purified PTFE aqueous dispersion. The method for producing a modified polytetrafluoroethylene powder of the present invention can remove or reduce the compound represented by general formula (1) or (2) present in the resulting modified polytetrafluoroethylene powder. The method for producing a polytetrafluoroethylene molded article of the present invention can remove or reduce the compound represented by general formula (1) or (2) present in the resulting polytetrafluoroethylene molded article. The composition of the present invention has the compound represented by general formula (3) removed or reduced.

[0016] The method for producing a purified PTFE aqueous dispersion of the present invention includes a step of removing or reducing the amount of a 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"). ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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.) Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specific examples include Na, K, and Li. ５ The four R's are 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. Also, it is preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. ５ In general formula (1), m may be 5 to 11. In general formula (2), n may be 6 to 12.

[0017] In this specification, unless otherwise specified, the term "organic group" refers to a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. Examples of the "organic group" include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, a formyl group, RaO-, RaCO-, and RaSO. ２ -, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, and RaOSO ２- (In these formulas, Ra is independently an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents). As the organic group, an alkyl group which may have one or more substituents is preferred. Furthermore, the organic group also includes those given above as examples of the substituent below. In this specification, unless otherwise specified, "substituent" means a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an 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 5- or 6-membered heterocycles 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, or an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, or 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 acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 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.

[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 includes alkylthio groups having a total of 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group, a carbamoylmethylthio group, and a t-butylthio group.

[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 2 to 9 carbon atoms in total, a dialkylcarbamoylamino group having 3 to 10 carbon atoms in total, an arylcarbamoylamino group having 7 to 13 carbon atoms in total, and a heterocyclic carbamoylamino group having 3 to 12 carbon atoms in total, preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 7 carbon atoms in total, a dialkylcarbamoylamino group having 3 to 6 carbon atoms in total, an arylcarbamoylamino group having 7 to 11 carbon atoms in total, and a heterocyclic carbamoylamino group having 3 to 10 carbon atoms in total, 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 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 fibrillating, or a low-molecular-weight PTFE that is melt-processable but not fibrillating. The standard specific gravity (SSG) and melt viscosity (MV), which are used as indicators of the molecular weight of PTFE, are not particularly limited.

[0036] As the above-mentioned modified monomer, there is no particular limitation as long as it can be copolymerized with TFE, and for example, can be listed perfluoroolefin such as hexafluoropropylene (HFP); chlorofluoroolefin such as chlorotrifluoroethylene (CTFE); hydrogen-containing fluoroolefin such as trifluoroethylene, vinylidene fluoride (VDF); perfluorovinyl ether; perfluoroalkylethylene; ethylene; the fluorine-containing vinyl ether with nitrile group etc. In addition, the modified monomer used can be one kind or multiple kinds.

[0037] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (X): ２ ═CF—ORf (X) (wherein Rf represents a perfluoroorganic group). In this specification, the term "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] Examples of the perfluorovinyl ether include perfluoro(alkyl vinyl ether) [PAVE], in which 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 perfluoromethyl vinyl ether (PMVE), in which the perfluoroalkyl group is a perfluoromethyl group, and purple perfluoropropyl 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 a modified monomer unit in the range of 0.0001 to 2 mol%, more preferably in the range of 0.0001 to less than 1 mol%, even more preferably in the range of 0.0001 to 0.5 mol%, and particularly preferably in the range of 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 using the powder for paste extrusion molding, 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 diluting a PTFE aqueous dispersion with water to a solids 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, to create a calibration curve, and 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. Examples of such modified PTFE include 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 a compound represented by the above general formula (1) or (2).

[0047] Methods for removing or reducing the compound represented by general formula (1) or (2) from the PTFE aqueous dispersion include adsorption treatment and concentration treatment. Alternatively, a method can be used in which the PTFE aqueous dispersion is dried and vaporized to remove or reduce the compound represented by general formula (1) or (2). The drying temperature can be, for example, the temperature of the heat treatment described below. Another method includes gasifying the PTFE aqueous dispersion and absorbing the compound represented by general formula (1) or (2) in the gas into an aqueous liquid using a droplet-type absorption device and / or a liquid film-type absorption device. 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 preferably 10 g or more, and more preferably 200 g or less, and more preferably 100 g or less.

[0049] Examples of the concentration treatment include phase separation concentration, electroconcentration, filtration using an ultrafiltration membrane, filtration using a reverse osmosis membrane (RO membrane), and nanofiltration. Examples of the concentration treatment include adding a nonionic surfactant to an aqueous PTFE dispersion to a concentration of 1% / PTFE or more, and then allowing the dispersion 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 dispersion is left standing is not limited, but may be, for example, 20°C or higher and 80°C or lower. The time period for leaving the dispersion is not limited, but may be, for example, 1 minute or longer and 24 hours or shorter.

[0050] The removal step preferably includes a step of subjecting the aqueous PTFE dispersion to an adsorption treatment and / or a concentration treatment, and more preferably a step of subjecting the aqueous PTFE dispersion to an ion exchange treatment and / or a concentration treatment. The ion exchange treatment and / or concentration treatment step may be a step of performing an ion exchange treatment, a concentration treatment, or a step of performing an ion exchange treatment and a concentration treatment, and each treatment may be performed multiple times. When performing an ion exchange treatment and a 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. It is more preferable that the ion exchange treatment and / or concentration treatment step be performed after the ion exchange 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 an aqueous PTFE dispersion is obtained using a hydrocarbon surfactant, the compounds represented by general formulas (1) and (2) are usually produced in an amount of 1 to 200 ppm relative to PTFE. The removal step removes or reduces the amount of the compound represented by general formula (1) or (2) in the aqueous PTFE dispersion, allowing a purified aqueous PTFE dispersion to be obtained.

[0053] The above-mentioned removal step is preferably to remove 80% by mass or more of the compounds represented by general formula (1) and (2) in the above-mentioned PTFE aqueous dispersion, more preferably to remove 85% by mass or more, even more preferably to remove 90% by mass or more, even more preferably to remove 95% by mass or more, particularly preferably to remove 97% by mass or more, particularly preferably to remove 98% by mass or more, and most preferably to remove 99% by mass or more.

[0054] 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 purified PTFE aqueous dispersion 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.

[0055] The PTFE aqueous dispersion can be obtained by a manufacturing method including the step of emulsion polymerization of 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, paraffin wax, etc.

[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 a compound represented by the following general formula (1) or (2) from a PTFE powder obtained using a hydrocarbon surfactant. General formula (1): (H-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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.) Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specific examples include Na, K, and Li. ５ The four R's are ５ may be the same or different. ５is 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 general formula (1), m may be 5 to 11. In general formula (2), n may be 6 to 12.

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

[0059] Methods for removing or reducing the compound represented by general formula (1) or (2) from the PTFE powder include heat treatment, fluorination treatment, and washing with water or an organic solvent. 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, isopropanol, etc. The organic solvents may be used in combination.

[0060] The heat treatment method is not particularly limited, and conventionally known methods can be used. The heat treatment temperature is preferably 150°C or higher. Furthermore, 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 a hydrocarbon surfactant at a temperature of 160°C or higher. The heat treatment temperature 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 heat 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, and particularly preferably 270°C or lower. The heat treatment may be accompanied by drying of moisture. That is, the heat treatment may be performed by 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 dried, water-free PTFE powder 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 for heat treatment. In this case, the drying may be performed below the above-mentioned temperature range, for example, below 150°C. The method for producing the modified PTFE powder of the present invention may include a step of coagulating a PTFE dispersion obtained using a hydrocarbon surfactant to obtain a wet PTFE powder containing water.

[0061] The fluorination treatment can be carried out by a conventional method. For example, the PTFE powder is exposed to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions. Fluorine radical sources include fluorine gas and CoF ３ , AgF ２ , U.F. ６ , OF ２ , N ２ F ２ , C.F. ３OF, halogen fluorides (e.g., IF, IF ３ , IF ５ , IF ７ etc.IF ｎ (n is 1 to 7); ClF, ClF ３ , BrF ３ etc.), rare gas fluorides (XeF ２ , XeF ４ , KrF ２ etc.), and nitrogen-containing fluorine compounds (e.g., NF ３ , N.F. ２ Among these, fluorine gas is most preferred due to its ease of handling, cost, ability to efficiently remove compounds represented by general formulas (1) and (2), and the fact that it is unlikely to produce new impurities such as iodine. Because 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 the fluorine radical source in the fluorine radical source / inert gas mixture can be 1 to 100% by volume, but is preferably 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 associated risk of fire.

[0062] 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 particularly preferably 150 ° C or higher. Also, particularly 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. Also, 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, particularly preferably 270 ° C or lower, particularly 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 in excess of 1000 ppb relative to PTFE. If the temperature is too high, the PTFE powder may easily be fibrillated even by a small shear force due to friction between the PTFE powder particles, and the original particle structure may be lost, which may result in a decrease in paste extrusion performance. The temperature for the fluorination treatment is preferably 110 to 270°C, more preferably 120 to 270°C, even more preferably 150 to 270°C, and particularly preferably 200 to 270°C.

[0063] 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 relative to 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 more 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 it may be uneconomical.

[0064] The suitable combination of the temperature of fluorination treatment and the amount of added fluorine radical source is that the temperature of heat treatment is above 100 ℃, and the amount of added fluorine radical source is, in terms of fluorine atom, 0.5 weight parts or more relative to 100 weight parts of raw material PTFE.As the above-mentioned combination, preferably above 100 ℃ and 1.0 weight parts or more, more preferably above 100 ℃ and 1.6 weight parts or more, more preferably above 100 ℃ and 2.0 weight parts or more, even more preferably above 100 ℃ and 2.5 weight parts or more, particularly preferably above 100 ℃ and 3.0 weight parts or more, particularly preferably above 100 ℃ and 5.0 weight parts or more. Also, 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. Also, 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. Also, 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. Also, 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.Also, 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. Also, 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. Also, 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. Also, 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.Further, 230 ° C or more and 0.5 parts by weight or more are preferable, 230 ° C or more and 1.0 parts by weight or more are more preferable, 230 ° C or more and 1.6 parts by weight or more are even more preferable, 230 ° C or more and 2.0 parts by weight or more are even more preferable, 230 ° C or more and 2.5 parts by weight or more are particularly preferable, 230 ° C or more and 3.0 parts by weight or more are particularly preferable, and 230 ° C or more and 5.0 parts by weight or more are most preferable. The heat treatment temperature in the above combination is preferably 310 ° C or less, more preferably 300 ° C or less, more preferably 290 ° C or less, even more preferably 280 ° C or less, particularly preferably 270 ° C or less, particularly preferably 250 ° C or less, and most preferably 240 ° C or less. The amount of fluorine radical source added in the above-mentioned combination, calculated as fluorine atom, is preferably 35.0 weight parts or less, more preferably 26.0 weight parts or less, even more preferably 20.0 weight parts or less, particularly preferably 15.0 weight parts or less, relative to 100 weight parts of raw material PTFE.In addition, the upper limit combination of heat treatment temperature and fluorine radical source is preferably 240 ℃ or less and 35.0 weight parts or less, more preferably 240 ℃ or less and 26.0 weight parts or less, even more preferably 240 ℃ or less and 20.0 weight parts or less, particularly preferably 240 ℃ or less and 15.0 weight parts or less.

[0065] The amount of fluorine radical source added (parts by weight) relative to 100 parts by weight of PTFE was calculated according to the following formula: A = (B / F) x 100 B = C x D x E C = {P / (RT x 1000)} x G x H A: Amount of fluorine radical source added (parts by weight) relative to 100 parts by weight of PTFE B: Total amount of fluorine radical source added (g) C: Concentration of fluorine radical source in 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 fluorine radical source (g / mol) H: Ratio of fluorine radical source in mixed gas In the above formulas, 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 the 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, the compounds represented by the general formulas (1) and (2) may be produced in an amount of 1 to 200 ppm relative to the PTFE. The removal step removes or reduces the amount of the compound represented by the general formula (1) or (2) in the PTFE aqueous dispersion, thereby allowing a modified PTFE powder to be obtained.

[0070] The above-mentioned removal step is preferably to remove 80% by mass or more of the compounds represented by the general formulas (1) and (2) in the above-mentioned PTFE powder, more preferably to remove 85% by mass or more, even more preferably to remove 90% by mass or more, even more preferably to remove 95% by mass or more, particularly preferably to remove 97% by mass or more, particularly preferably to remove 98% by mass or more, and most preferably to remove 99% by mass or more. The above-mentioned removal step is preferably to reduce the content of the compounds represented by the general formulas (1) and (2) in the obtained modified PTFE powder to 500 ppb or less, more preferably to reduce to 200 ppb or less, more preferably to reduce to 100 ppb or less, particularly preferably to reduce to 50 ppb or less, and most preferably to reduce to 25 ppb or less.

[0071] The present invention relates to a method for producing a molded article using PTFE produced using a hydrocarbon surfactant, the method comprising the step of removing or reducing the amount of a compound represented by the following general formula (1) or (2): General formula (1): (H-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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.) Examples of the metal atom include monovalent and divalent metal atoms, such as alkali metals (Group 1) or alkaline earth metals (Group 2), and specific examples include Na, K, and Li. ５ The four R's are 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 general formula (1), m may be 5 to 11. In 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 amount of the compound represented by formula (1) or (2) include heat treatment, fluorination treatment, and the like.

[0074] The heat treatment method is not particularly limited, and conventionally known methods 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 heat treatment step at a temperature of 160°C or higher. The heat treatment temperature 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 heat 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, and particularly preferably 270°C or lower. The heat treatment time is not particularly limited, but is, for example, 1 minute or longer and 24 hours or shorter. The heat treatment may be accompanied by drying. During drying, the compound represented by general formula (1) or (2) and the compound represented by general formula (7) described below are reduced.

[0075] The fluorination treatment can be carried out by a conventional method. For example, the PTFE powder is exposed to a fluorine radical source that generates fluorine radicals under fluorination treatment conditions. Fluorine radical sources include fluorine gas and CoF ３ , AgF ２ , U.F. ６ , OF ２ , N ２ F ２ , C.F. ３ OF and halogen fluorides, such as IF ５ , ClF ３ , BrF ３and the like. Because 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 the fluorine radical source in the fluorine radical source / inert gas mixture can be 1 to 100% by volume, but is preferably 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 associated risk of fire. The heat treatment and fluorination treatment may be performed 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), which will be described later.

[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 of the fluorination treatment is not particularly limited, but is, for example, 1 minute or longer and 24 hours or shorter.

[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, more preferably, it is 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, particularly 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 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. Even if the amount of the fluorine radical source added is too large, the fluorination effect will not be improved, and it 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 the 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] The method for producing a molded body of the present invention may further include, in addition to the removal step, a step (1a) of mixing the PTFE powder obtained using a hydrocarbon surfactant with an extrusion aid, a step (1b) of paste-extrusion molding the resulting mixture, a step (1c) of drying the extrudate obtained by extrusion molding, and a step (1d) of calcining the dried extrudate to obtain a molded body. 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 higher than 310°C, and in that case, the heat treatment is preferably performed at 500°C or less. The removal step may also be performed during step (1b), step (1c), or step (1d). The removal step may be performed multiple times. For example, the removal step may be performed two, three, four, five, six, seven, eight, nine, or ten times. The above-mentioned heat treatment and fluorination treatment can be carried out in combination, or can be carried out simultaneously.As described above, in the manufacturing method of the molded body of the present invention, the removing step can be to remove or reduce the compound represented by general formula (1) or (2) from the PTFE powder obtained by using hydrocarbon surfactant, or to remove or reduce the compound represented by general formula (1) or (2) from the molded body molded by using the PTFE powder obtained by using hydrocarbon 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] The manufacturing method of the molded body of the present invention can also comprise, in addition to above-mentioned removing step, the step (2a) of mixing the PTFE powder obtained by using hydrocarbon surfactant with extrusion aid, the step (2b) of extrusion rolling the mixture obtained, the step (2c) of drying the extrudate obtained by extrusion rolling, the step (2d) of uniaxially stretching the extrudate after drying, the step (2e) of biaxially stretching the uniaxially stretched stretched material, the step (2f) of firing the stretched material after biaxial stretching, and the step (2g) of laminating the fired material with other materials.In this case, above-mentioned removing step can be carried out after step (2a) before step (2b), after step (2b) before step (2c), after step (2c) before step (2d), after step (2d) before step (2e), after step (2e) before step (2f), after step (2f) 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. Heat treatment and fluorination treatment may be carried out in combination.

[0085] In the manufacturing method of the molded article of the present invention, the above-mentioned removal step is preferably to remove 80% or more by mass of the compounds represented by general formula (1) and (2) before and after the removal step, more preferably to remove 85% or more by mass, even more preferably to remove 90% or more by mass, even more preferably to remove 95% or more by mass, particularly preferably to remove 97% or more by mass, particularly preferably to remove 98% or more by mass, and most preferably to remove 99% or more by mass.The above-mentioned removal step is preferably to make the content of the compounds represented by general formula (1) and (2) in the obtained PTFE molded article be 500 ppb or less, more preferably to make 200 ppb or less, more preferably to make 100 ppb or less, particularly preferably to make 50 ppb or less, and most preferably to make 25 ppb or less.

[0086] As mentioned above, one of the preferred methods for removing or reducing the compound represented by general formula (1) or (2) is 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 above 100°C to remove or reduce the compound represented by the following general formula (1) or (2): General formula (1): (H-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) ｑ M ２ (wherein n is 4 to 20. M ２ is H, metal atom, NR５ ４ (R ５may be the same or different and are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. q is 1 or 2.) By contacting with a 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, by contacting with a fluorine radical source at the above-mentioned specific temperature, such impurities can also be removed. The temperature when contacting with the fluorine radical source is above 100°C. The temperature when the fluorine radical source is brought into contact 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, it is more preferably 210°C or higher, especially preferably 220°C or higher, and most preferably 230°C or higher. Also, it 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 production method, the amount of fluorine radical source added and the combination of temperature and amount added can all be those described above. When a fluorine radical source is contacted in the above-mentioned method for producing modified PTFE, various conditions for fluorination treatment (for example, the type of fluorine radical source, the amount of fluorine radical source added, the 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 for contacting a fluorine radical source, the removal method explained in the removal step, such as heat treatment or washing with water or an organic solvent, may be combined. In particular, a heat treatment step may be carried out after the step of contacting a fluorine radical source to remove or reduce the compound represented by general formula (1) or (2).By carrying out the heat treatment step, the content of the compounds represented by the general formulas (1) and (2) can be further reduced. Also, the content of the compound represented by the general formula (7) can be further reduced. The heat treatment temperature and time in the heat treatment step can be within the above-mentioned ranges. In the method for producing the modified PTFE, the PTFE obtained by using the hydrocarbon surfactant can be in the form of a powder or a molded product.

[0087] As mentioned above, fluorination treatment using a specific amount of a fluorine radical source is also one preferred embodiment of a method for removing or reducing the compound represented by general formula (1) or (2). That is, the present invention also relates to 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 relative to 100 parts by weight of PTFE, calculated as fluorine atoms. General formula (1): (H-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) ｑ M ２ (wherein n is 4 to 20. M ２ is H, metal atom, NR ５ ４ (R ５are the same or different and are H or an organic group having 1 to 10 carbon atoms), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. q is 1 or 2. By contacting the fluorine radical source in the above-mentioned specific amount (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 other than the compound represented by general formula (1) or (2), such as decomposition products of substances used in the polymerization of PTFE. However, by contacting the fluorine radical source in the above-mentioned specific amount, such impurities can also be removed. The amount of the fluorine radical source added is 0.5 parts by weight or more per 100 parts by weight of the raw material PTFE, calculated as fluorine atoms. Preferably, it is 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 is not improved, and the process tends to be uneconomical. In this production method, the fluorination treatment temperature and the combination of temperature and amount can all be used. When a fluorine radical source is contacted in the above-mentioned method for producing modified PTFE, various conditions (for example, the type of fluorine radical source, the temperature of the fluorination treatment, the timing and number of times of the 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. In addition to the method for contacting a fluorine radical source, the removal method explained in the removal step, such as heat treatment or washing with water or an organic solvent, may be combined.In particular, a heat treatment step may be carried out after the step of contacting a fluorine radical source to remove or reduce the compound represented by general formula (1) or (2). By carrying out 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 heat treatment temperature and time in the heat treatment step can be within the ranges described above. In the method for producing the modified PTFE, the PTFE obtained using the hydrocarbon surfactant may be in the form of a powder or a molded product.

[0088] Specific hydrocarbon surfactants are described below.

[0089] Hydrocarbon surfactants have a hydrophilic portion and a hydrophobic portion on the same molecule. They 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 include 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) 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 The Dow Chemical Company; and 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 from Resolution Performance Products and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0104] Examples of hydrocarbon surfactants include R-L-M 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 ring. L is -ArSO ３ － , -SO ３ － , -SO ４ -, -PO ３ － or -COO － and M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. ３ － is an aryl sulfonate. ) Specific examples of anionic surfactants include those represented by CH ３ - (CH２ ) ｎ -L-M １ (wherein n is an integer of 6 to 17, and L and M are the same as above). Mixtures in which R is an alkyl group having 12 to 16 carbon atoms and L is sulfate or sodium dodecyl sulfate (SDS) can also be used. Examples of hydrocarbon surfactants include those represented by the formula: ６ (-L-M １ ) ２ (In the formula, R ６ is a linear or branched alkylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms which may have a substituent, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocycle or may be a ring. ３ － , -SO ３ － , -SO ４ -, -PO ３ － or -COO － and M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. ３ － is an aryl sulfonate. Examples of hydrocarbon surfactants include anionic surfactants represented by the formula: ７ (-L-M １ ) ３ (In the formula, R ７ is a linear or branched alkylidyne group having 1 or more carbon atoms which may have a substituent, or a cyclic alkylidyne group having 3 or more carbon atoms which may have a substituent, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may be a ring. ３ － , -SO ３ － , -SO ４ -, -PO３ － or -COO － and M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. ３ － 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 atoms are entirely hydrocarbon. These siloxane surfactants can also be considered hydrocarbon surfactants in the sense that the carbon atoms of the hydrocarbyl groups are entirely substituted with hydrogen atoms, where the carbon atoms may be substituted with 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 contain one or more polar moieties containing ionic groups such as sulfates, sulfonates, phosphonates, phosphate esters, carboxylates, carbonates, sulfosuccinates, taurates (as free acids, salts, or esters), phosphine oxides, betaines, betaine copolyols, and quaternary ammonium salts. The ionic hydrophobic portion may also contain ionically functionalized siloxane grafts. Examples of such siloxane surfactants include polydimethylsiloxane-grafted (meth)acrylates, polydimethylsiloxane-grafted polyacrylate salts, and polydimethylsiloxane-grafted quaternary amines. The polar portion of the hydrophilic portion of the siloxane surfactant may contain 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) can 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] Examples of anionic hydrocarbon surfactants include the sulfosuccinate surfactant Lankropol® K8300 from Akzo Nobel Surface Chemistry LLC. Examples of sulfosuccinate hydrocarbon surfactants include diisodecyl sulfosuccinate sodium salt (Emulsogen® SB10 from Clariant) and diisotridecyl sulfosuccinate sodium salt (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): (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 represented by the general formula: -Y-R ６ a group represented by R ２ and R ５ At least one of the groups is a group represented by the general formula: -X-A or a group represented by the general formula: -Y-R ６ In addition, X, which may be the same or different in each occurrence, represents a divalent linking group or a bond; A, which may be the same or different in each occurrence, represents -COOM, -SO ３ M or -OSO ３ M (M is H, metal atom, NR ７ ４, optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ is H or an organic group); Y is the same or different in each occurrence and is —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 R may be the same or different in each occurrence and 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; 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 represented by the general formula: -Y-R ６ a group represented by R ２ and R ５ At least one of the groups is a group represented by the general formula: -X-A or a group represented by the general formula: -Y-R ６ R represents a group represented by the formula: 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 as the 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 １The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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 have a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent is even more preferred, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) is most preferred.

[0119] The monovalent substituent is a group represented by the general formula: -Y-R ６ a group represented by the general formula: -X-A, -H, optionally substituted C １－２０ an alkyl group of —NH ２ , -NHR ９ (R ９ is an organic group), —OH, —COOR ９ (R ９ is an organic group) or -OR ９ (R ９ The alkyl group preferably has 1 to 10 carbon atoms.

[0120] R ９ As for C １－１０ or an alkyl group of C １－１０ The alkylcarbonyl group represented by the formula C is preferred. １－４ or an alkyl group of C １－４An 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 a bond. ６ 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 is -CO-, -S(=O) ２ -, -O-, -COO-, -OCO-, -S (=O) ２ -O-, -O-S (=O) ２ --, --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 the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ The organic group is more preferably H.

[0124] In the formula, A is the same or different in each occurrence and is -COOM, -SO ３ M or -OSO ３ M (M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ７ is H or an organic group. ７ may be the same or different.

[0125] R ７ As the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ The metal atom is preferably a monovalent or divalent metal atom, such as an alkali metal (Group 1) or an alkaline earth metal (Group 2), and is preferably Na, K, or Li.

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

[0127] wherein Y in each occurrence is the same or different and is —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—, or —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 the group, H or C １－１０ is preferably an organic group represented by the formula: １－４ The organic group is more preferably H.

[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, more preferably 2 to 10 carbon atoms.

[0131] R ６The alkyl group of R may contain one or more groups selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms, but does not contain these groups at the terminal of the alkyl group. ６ The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0132] R ６ As the general formula: -R １０ -CO-R １１ a group represented by the general formula: -R １０ -COO-R １１ a group represented by the general formula: -R １１ a group represented by the general formula: -R １０ -NR ８ CO-R １１ or a group represented by the general formula: -R １０ -CONR ８ -R １１ (wherein 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. ６ As the general formula: -R １０ -CO-R １１ A group represented by the following formula is more preferred.

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

[0134] R １０ The number of carbon atoms in the alkylene group of R is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. 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 of may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, even more preferably 1 to 10, still 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] As the surfactant (1), 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) is preferred, and a compound represented by general formula (1-1) or a compound represented by general formula (1-2) is more preferred.

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

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

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

[0140] The group represented by the general formula -X-A includes: -COOM, -R １２ COOM, -SO ３ M, -OSO ３ M, -R １２ SO ３ M, -R １２ OSO ３ M, -OCO-R１２ -COOM, -OCO-R １２ -SO ３ M, -OCO-R １２ -OSO ３ M-COO-R １２ -COOM, -COO-R １２ -SO ３ M, -COO-R １２ -OSO ３ M, -CONR ８ -R １２ -COOM, -CONR ８ -R １２ -SO ３ M, -CONR ８ -R １２ -OSO ３ M, -NR ８ CO-R １２ -COOM, -NR ８ CO-R １２ -SO ３ M, -NR ８ CO-R １２ -OSO ３ M, -OS (=O) ２ -R １２ -COOM, -OS (=O) ２ -R １２ -SO ３ M, or -OS (=O) ２ -R １２ -OSO ３ M (wherein, R ８ and M are as above. １２ is C １－１０ The alkylene group represented by the formula (I) is preferred. 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: -Y-R ６ Examples of the group represented by the general formula: -R １０ -CO-R １１ A group represented by the general formula: -OCO-R１０ -CO-R １１ A group represented by the general formula: -COO-R １０ -CO-R １１ A group represented by the general formula: -OCO-R １０ -COO-R １１ A group represented by the general formula: -COO-R １１ a group represented by the general formula: -NR ８ CO-R １０ -CO-R １１ or a group represented by the general formula: -CONR ８ -R １０ -NR ８ CO-R １１ (wherein R ８ , R １０ and R １１ is as described above.) is preferred.

[0142] In the formula, R ４ and R ５ is independently H or C １－４ The alkyl group represented by the formula R ４ and R ５ The alkyl group may have 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

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

[0144] R in the general formula (1-3) ２ is preferably H, OH or an optionally substituted C １－２０ alkyl group, more preferably H, OH or an unsubstituted C １－２０ alkyl group, and even more preferably H or OH. In the above R ２ alkyl group, up to 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, up to 50% may be substituted by halogen atoms, and up to 25% may be substituted by halogen atoms, but it is preferably a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms.

[0145] The surfactant (1) is obtained by reacting a carboxylic acid represented by the formula: R ６ -COOH (wherein R ６ is as described above.) with a halogenating agent to obtain a carboxylic acid halide represented by the formula: R ６ -COZ (wherein R ６ is as described above. Z is a halogen atom.), and the above carboxylic acid halide is reacted with a compound represented by the formula: (wherein R ３ to R ５ , X and A are as described above. Z １１ is -CH ２ O-, -O- or -NH-.) to obtain a compound (12) represented by the formula: (wherein R ３ to R ６ , X, A and Z １１ are as described above.). It can be preferably produced by a production method including step (12).

[0146] As R ３ in the formula of the above acid compound, a group represented by the general formula: -Z １１ H (wherein Z １１ is as described above.), or -H is preferable. When R ３ is a group represented by the general formula: -Z １１ H, in step (12), the above group reacts with the above carboxylic acid halide, and the general formula: -Z １１ -CO-R ６ (wherein R ６and Z １１ is as above.) A group represented by the formula:

[0147] Examples of the halogenating agent used in step (11) include oxalyl chloride, thionyl chloride, diethylaminosulfur trifluoride (DAST), deoxofluor, 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), with ethyl acetate being 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. Also, it is 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, relative to 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 a compound represented by the formula: (In the formula, R １ ~R ５ is as above. Z １１ Ha-CH ２ and a compound (20) represented by the formula: (wherein n is an integer of 1 to 5) to form a compound represented by the formula: (In the formula, R １ ~R ５ , Z １１ , M and n are as defined above.

[0168] R in the formula of compound (20) ２ As the general formula: -Z １１ H (in the formula, Z １１ is as defined above.) or —H is preferred. ２ is represented by 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 represented by the general formula: -Z１１ -CO-(CH ２ ) ｎ -COOM (in the formula, Z １１ , M and n are as defined above.) is produced. Compound (20) may be a hydrochloride, a 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 the 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 the 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 more 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 a compound represented by the formula: (In the formula, R ４ and R ５ is as defined above.) and a tartaric acid ester represented by the formula: R ６ R ８ -NH (wherein, R ６ and R ８ is as defined above.) to react with an amine represented by the formula: (In the formula, R ４ ~R ６ and R ８ is as described above.), and reacting compound (31) with a compound of the formula: (wherein M is as defined above) to react with a sulfonic acid chloride represented by the formula: (In the formula, R ４ ~R ６ , R ８ and M is as defined above.)

[0177] In the 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, still 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 the yield and reducing waste.

[0178] The reaction in step (31) can be carried out in a solvent. The solvent is 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 0.1 to 72 hours, more preferably 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 moles, more preferably 1.6 to 20 moles, of the sulfonic chloride relative to 1 mole 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 moles, more preferably 1.0 to 20 moles, per mole 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 a compound represented by the formula: (In the formula, R １ and R ３ ~R ５ is as described above.) and an alcohol represented by the formula: (wherein n is an integer of 1 to 5) to form a compound represented by the formula: (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 step (41) is preferably 0 to 5 MPa, more preferably 0.1 to 1 MPa.

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

[0207] The surfactant (1) may also be a compound represented by the formula: (In the formula, R ４ and R ５ is as defined above.) and a tartaric acid ester represented by the formula: R ６ R ８ -NH (wherein, R ６ and R ８ is as defined above.) to react with an amine represented by the formula: (In the formula, R ４ ~R ６ and R ８ is as described above.), and reacting compound (31) with the compound (31) of the formula: (wherein n is an integer of 1 to 5) to form a compound represented by the formula: (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 step (51) is preferably 0 to 5 MPa, more preferably 0.1 to 1 MPa.

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

[0215] The surfactant (1) may also be a compound represented by the formula: R ６ -OH (wherein, R ６ is as described above.) is reacted with fumaric acid halide to obtain a compound represented by the formula: (In the formula, R ６ as described above.), and reacting the compound (61) with a sulfonating agent such as sodium hydrogen sulfite to obtain a compound represented by the formula: (In the formula, R ６ and X is 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), with ethyl acetate being 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 step (61) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.

[0228] The reaction time in step (61) is preferably 0.1 to 72 hours, more preferably 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 a compound represented by the formula: (In the formula, R １０ , R １１ and Y are as defined above.) is converted into a compound (70) represented by the formula: (In the formula, R １０ , R １１ and Y are as described above. １００ is -OH or -OSO ３ M. 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. The solvent is 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 step (71) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

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

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

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

[0249] R １００ The alkyl group as R １００ -CH ２ - as described above, 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 ２ ) 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 0.1 to 72 hours, more preferably 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 the 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 the method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0275] In step (102), the compound (101) can be oxidized using, for example, (a) Jones reagent (CrO ３ / H ２ SO ４(b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method using NiCl ２ (e) a method of treating with a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as Al(CH ３ ) ３ , Al[OCH(CH ３ ) ２ ] ３ and a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted with the compound in the presence of an aluminum catalyst such as (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 pressure for oxidation in 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: (In the formula, R １０ , R １１ and Y are as described above. １０１ is an organic group.) to obtain compound (70) by ozonolysis (201).

[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 the step (201) can be carried out by reacting the 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. The solvent is preferably water or an organic solvent, and examples thereof include water, alcohols, 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 step (201) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

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

[0298] The time for ozonolysis in 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: (In the formula, R １０ and Y are as described above. １００ is an alkyl group.) is epoxidized to give a compound (300) represented by the formula: (In the formula, R １０ , R １００ and Y are as defined above.), １０２ ２ CuLi(R １０２ is an alkyl group) to form a dialkyl copper lithium represented by the formula: (In the formula, R １０ , R １００ , R １０２and Y are as described above. The compound (70) can be produced by a production method including a step (302) of obtaining a compound (302) represented by the formula:

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

[0301] Two 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-butylhydroperoxoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, etc. Among these, peracids are preferred, and metachloroperbenzoic acid is 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. The solvent is preferably an organic solvent, such as a ketone, an ether, a halogenated hydrocarbon, an aromatic hydrocarbon, a nitrile, pyridine, a nitrogen-containing polar organic compound, or dimethyl sulfoxide, 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 step (301) is preferably from -78 to 200°C, more preferably from -40 to 150°C.

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

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

[0314] In step (302), the dialkyl copper lithium can be used in an amount of 0.5 to 10.0 moles per mole of 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), the compound (302) can be oxidized using, for example, (a) Jones reagent (CrO ３ / H ２ SO ４ (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method using NiCl ２ (e) a method of treating with a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as Al(CH ３ ) ３ , Al[OCH(CH ３ ) ２ ] ３ and a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted with the compound in the presence of an aluminum catalyst such as (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 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: (In the formula, R １０ and Y are as described above. １００is 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; ２ O ２ , MnO ２ , KMnO ４ , RuO ４ , m-chloroperbenzoic acid, oxygen, etc., or a combination 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), with ethyl acetate being 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 step (401) is preferably from -78 to 200°C, more preferably from -20 to 150°C.

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

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

[0351] Compound (100), compound (300) and compound (400) have the formula: (In the formula, R １０ and Y are as described 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:

[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. The solvent is 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 step (501) is preferably from -78 to 200°C, more preferably from -20 to 100°C.

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

[0361] The reaction time in 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, if the obtained compound does not contain —COOH, —SO ３ H, -OSO ３ In the case of compounds where M is H, such as H, 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). Alternatively, a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups) to radical treatment or oxidation treatment can also be used. The radical treatment is any treatment that generates radicals in a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). For example, it is a treatment in which deionized water and a hydrocarbon surfactant are added to a reactor, the reactor is sealed, the system is purged with nitrogen, the reactor is heated and pressurized, a polymerization initiator is added, the mixture is stirred for a certain period of time, and the reactor is depressurized to atmospheric pressure and then cooled. The oxidation treatment is a treatment in which an oxidizing agent is added to a hydrocarbon surfactant having one or more carbonyl groups (excluding carbonyl groups in carboxyl groups). Examples of the oxidizing agent 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) includes a hydrocarbon surfactant represented by the formula: R-X (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 -OSO ３ X １ , -COOX １ or -SO ３ X １ (X １ represents H, a metal atom, NR １ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R １are 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): (In the formula, R １ａ R is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, in which a hydrogen atom bonded to a carbon atom may be substituted with a monovalent organic group containing a hydroxy group or an ester bond, and when it has 2 or more carbon atoms, it may contain a carbonyl group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or form a ring. ２ａ and R ３ａ are independently a single bond or a divalent linking group. １ａ , R ２ａ and R ３ａ has a total of 6 or more carbon atoms. ａ represents H, a metal atom, NR ４ａ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ａ are H or organic groups and may be the same or different. １ａ , R ２ａ and R ３ａ any two of which may be bonded to each other to form a ring; a surfactant (a) represented by the following formula (b): (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 represents H, a metal atom, NR ５ｂ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ５ｂ are H or organic groups and may be the same or different. １ｂ , R ２ｂ , R ３ｂ and R ４ｂ Any two of the groups may be bonded to each other to form a ring. L represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｂ -B-*, -NR ６ｂ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｂ -B-, -NR ６ (excluding the carbonyl group contained in CO—B—), 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. * represents -OSO ３ X ｂ (b) a surfactant represented by the following formula (c): (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 are independently a single bond or a divalent linking group. １ｃ , R ２ｃ and R ３ｃ has a total of 5 or more carbon atoms. ｃ Ha, -COOX ｃ or -SO ３ X ｃ (X ｃ represents H, a metal atom, NR ４ｃ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ｃ are H or organic groups, and may be the same or different. １ｃ , R ２ｃ and R ３ｃ any two of which may be bonded to each other to form a ring; and a surfactant (c) represented by the following formula (d): (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 is -SO ３ X ｄ or -COOX ｄ (X ｄ represents H, a metal atom, NR ５ｄ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and 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 the groups may be bonded to each other to form a ring. L represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ(excluding the carbonyl group contained in CO—B—), 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. 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 one or more carbon atoms, or a cyclic alkyl group having three 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. That is, CH ３ The alkyl group also includes acyl groups such as an acetyl group represented by -C(=O)-. 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. R 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 heterocyclic ring. ３ —C(═O)—CH ２ The group represented by - has 3 carbon atoms, and ３ -C(=O)-C ２ H ４ -C(=O)-C ２ H ４ The group represented by - has 7 carbon atoms, and CH ３ The group represented by —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, 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. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０１ａ (In the formula, R １０１ａ The alkyl group may be one in which 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms are 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. ２ａ and R ３ａ are preferably each 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. 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, 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. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０２ａ (In the formula, R １０２ａ 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 ３ａ R has a total number of carbon atoms of 6 or more. The total number of carbon atoms 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. 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 represents H, a metal atom, NR ４ａ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and 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 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 ａ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ４ａ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ａ NH ４ In this case, 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 １ａAs 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 compound, the compound of the formula: (In the formula, n １１ａ is an integer from 0 to 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 from 2 to 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 R preferably does not contain a carbonyl group. １１ａ In the alkyl group as defined 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. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０３ａ (In the formula, R １０３ａ is an alkyl group). １１ａ The alkyl group as above may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkyl group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0377] R １２ａ is an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3. １２ａ The alkylene group as R may be linear or branched. １２ａ The alkylene group as R preferably does not contain a carbonyl group. １２ａ Examples of the alkyl group include an ethylene group (-C ２ H ４ -) or propylene group (-C ３ H ６ -) is more preferred. １２ａ In the alkylene group represented by the formula: １０４ａ (In the formula, R １０４ａ is an alkyl group). １２ａ The alkylene group as the above may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0378] R ２ａ and R ３ａ is 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 ２ H ４ -) or propylene group (-C ３ H ６ -) is more preferred.

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

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[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: (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 ３ Si-Cl (wherein R ２０１ａ are independently an alkyl group or an aryl group. (In the formula, R ３ａ , R ２０１ａ and E ａ is as described above.), and reacting compound (11a) with compound (11a) of the formula: (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: (In the formula, R １ａ , R ２１ａ , R ３ａ and E ａ is as described above.), and a step (12a) of obtaining a compound (12a) represented by the formula: (In the formula, R １ａ , R ２１ａ and R ３ａis as described above.), and reacting compound (13a) with a compound of the formula: (In the formula, X ａ is as described above.) to give a sulfonic acid chloride represented by the formula: (In the formula, R １ａ , R ２１ａ , R ３ａ and X ａ is 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: 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 compound (10a) in step (11a) is preferably −100 to 0° C., more preferably −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 compound (10a) in 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 and compound (10a) in 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 products.

[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 cesium fluoride, potassium fluoride, or lithium fluoroborate (LiBF ４ ), a method using an inorganic salt such as 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 the 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). Of 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 the completion of the reaction. After adding water to the solution, the solution is allowed to stand to separate into two phases, and the aqueous phase is recovered. The solvent is then distilled off to recover high-purity compound (14a). Compound (14a) may be -OSO ３ When the compound has a group represented by H (i.e., when X is H), an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia is used instead of water to obtain -OSO ３ It is also possible to convert H to a sulfate group.

[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: (In the formula, R ３ａ As mentioned above, R ２２ａ is a monovalent organic group, E ａ is a leaving group.) and a ketone represented by the formula: (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: (In the formula, R １ａ , R ３ａ and E ａ As mentioned above, R ２４ａ is a single bond or a divalent linking group.), and a step (21a) of obtaining a compound (21a) represented by the formula: (In the formula, R １ａ , R ２４ａ and R ３ａ is as described above.), and reacting compound (22a) with compound (22a) of the formula: (In the formula, X ａ is as described above.) to give a sulfonic acid chloride represented by the formula: (In the formula, R１ａ , R ２４ａ , R ３ａ and X ａ is as described above.

[0427] 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.

[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 R is preferably a linear or branched alkyl group having one or more carbon atoms, and more preferably a methyl group. ２３ａ R is preferably a linear or branched alkyl group having one or more carbon atoms, and more preferably a methyl group. ２４ａ As the alkyl group, a linear or branched alkylene group having one or more carbon atoms is preferred, and a methylene group (—CH ２ -) 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 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 cesium fluoride, potassium fluoride, or lithium fluoroborate (LiBF ４ ), a method using an inorganic salt such as 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 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 the 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). Of 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 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 the completion of the reaction. After adding water to the solution, the solution is allowed to stand to separate into two phases, and the aqueous phase is recovered. The solvent is then distilled off to recover high-purity compound (23a). Compound (23a) may be -OSO ３ When the compound has a group represented by H (i.e., when X is H), an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia is used instead of water to obtain -OSO ３ It is also possible to convert H to a sulfate group.

[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 represented by the formula: (In the formula, R １ａ is as described above.) to form a compound represented by the formula: (In the formula, R １ａ , R ３ａ and E ａ is as described above.), and a step (31a) of obtaining a compound (31a) represented by the formula (In the formula, R １ａ , R ３ａ and E ａ is as described above.), and a step (32a) of obtaining a compound (32a) represented by the formula: (In the formula, R １ａ and R ３ａ is as described above.), and reacting compound (33a) with a compound of the formula: (In the formula, X ａ is as described above.) to give a sulfonic acid chloride represented by the formula: (In the formula, R １ａ , R ３ａ and X ａ is 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 ａrepresents 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 the 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 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 (CF ３ CO ２ ) ３ ]・H ２ O (wherein, Cn ＊ represents 1,4,7-trimethyl-1,4,7-triazabicyclononane) to (NH ４ ) ２ Ce(NO ３ ) ６ and trifluoroacetic acid followed by the addition of sodium perchlorate to form a complex in a nitrile solvent.

[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 cesium fluoride, potassium fluoride, or lithium fluoroborate (LiBF ４ ), a method using an inorganic salt such as 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 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 the 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). Of 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 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 the completion of the reaction. After adding water to the solution, the solution is allowed to stand to separate into two phases, and the aqueous phase is recovered. The solvent is then distilled off to recover high-purity compound (34a). ３ When the compound has a group represented by H (i.e., when X is H), an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia is used instead of water to obtain -OSO ３ It is also possible to convert H to a sulfate group.

[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: (In the formula, R １ａ As mentioned above, R ２１ａ is a single bond or a divalent linking group.) and an alkene represented by the formula: (In the formula, Y ５１ａ is an alkoxyl group.) to form a compound represented by the formula: (In the formula, R１ａ and R ２１ａ is as described above.) and a step (41a) of obtaining a compound (41a) represented by the formula: (In the formula, X ａ is as described above.) to give a sulfonic acid chloride represented by the formula: (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 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 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 the 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 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. The solvent is 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). Of 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 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 the completion of the reaction. After adding water to the solution, the solution is allowed to stand to separate into two phases, and the aqueous phase is recovered. The solvent is then distilled off to recover high-purity compound (42a). Compound (42a) may be -OSO ３ When the compound has a group represented by H (i.e., when X is H), an alkaline aqueous solution such as an aqueous sodium hydrogen carbonate solution or aqueous ammonia is used instead of water to obtain -OSO ３ It is also possible to convert H to a sulfate group.

[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 １ｂR 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 heterocycle, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, and an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include 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 １ｂ The substituent that the alkyl group as the 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 the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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 １ｂAs the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent is preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms which does not contain a carbonyl group is more preferred, a linear or branched alkyl group having 1 to 10 carbon atoms which does not have a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent is even more preferred, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) 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 ４ｂ The substituent as is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methyl group or an ethyl group.

[0514] R ２ｂ and R ４ｂ The alkyl group as the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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 ４ｂThe alkyl group as the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred.

[0516] R ２ｂ and R ４ｂ are each independently preferably H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and ３ ) or an ethyl group (-C ２ H ５ ) is even more preferred, with H being especially preferred.

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

[0518] The alkylene group preferably does not contain a carbonyl group. The alkylene group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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, and more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and a methylene group (—CH ２ -), ethylene group (-C ２ H ４ -), isopropylene group (-CH(CH ３ ) CH ２ -) or propylene group (-C ３ H ６ -) is more preferred.

[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, and more preferably 0 or 1. q is preferably an integer of 0 to 10, and 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 represents H, a metal atom, NR ５ｂ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and 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 X may be as defined above. ｂ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ５ｂ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ｂ NH ４ In this case, 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, —CO ２ -B-*, -OCO-B-*, -CONR ６ｂ -B-*, -NR ６ｂ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｂ -B-, -NR ６ (excluding the carbonyl group contained in CO—B—), 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. ６is more preferably H or a methyl group. ３ X 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: (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 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 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, with the concentration of heavy water being 4.79 ppm.

[0532] The surfactant (b) may be, for example, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OCH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ NHC(O)CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OC(O)CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ H, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ OSO ３ Li, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ K, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ NH ４ CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH(CH ３ ) ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OCH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ NHC(O)CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OC(O)CH ２ CH ２ OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OSO ３ Na, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ H, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Li, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ K, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH２ OSO ３ NH ４ , C.H. ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OSO ３ Na and the like.

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

[0534] The surfactant (b) is represented by the following formula: １１ｂ -CH=CH-(CR ２ｂ ２ ) ｎ - (OR ３ｂ ) ｐ - (CR ４ｂ ２ ) ｑ -L-OH (wherein, R ２ｂ ~R ４ｂ , n, p and q are as defined above. 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 to form a ring. L is a single bond, -CO ２ -B-*, -OCO-B-*, -CONR ６ｂ -B-*, -NR ６ｂ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｂ -B-, -NR ６ｂ(excluding the carbonyl group contained in CO—B—), 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 give a compound (10b) represented by the following formula: (In the formula, L, R ２ｂ ~R ４ｂ , R １１ｂ , n, p and q are as defined above.), and oxidizing compound (11b) to obtain a compound represented by the following formula: (In the formula, L, R ２ｂ ~R ４ｂ , R １１ｂ , n, p and q are as defined above), and a step (12b) of converting compound (12b) into a sulfate ester to obtain a compound represented by the following formula: (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:

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

[0536] R １１ｂis preferably H, 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, more preferably H, 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, still more preferably H, or a linear or branched alkyl group having 1 to 9 carbon atoms which does not have a substituent, and ３ ) or an ethyl group (-C ２ H ５ ) is even more preferred, H or a methyl group (—CH ３ ) is particularly preferred, with H being most preferred.

[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 ２ ) 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 0.1 to 72 hours, more preferably 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 the 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 the method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0562] In step (12b), the compound (11b) can be oxidized using, for example, (a) Jones reagent (CrO ３ / H ２SO ４ (b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method using NiCl ２ (e) a method of treating with a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as Al(CH ３ ) ３ , Al[OCH(CH ３ ) ２ ] ３ and a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted with the compound in the presence of an aluminum catalyst such as (Oppenauer oxidation).

[0563] The oxidation in step (12b) can be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include 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 pressure for oxidation in 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 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: (In the formula, L, R １ｂ ~R ４ｂ , n, p and q are as defined above. １０１ｂ is an organic group.) is subjected to ozonolysis to obtain a compound (20b) represented by the following formula: (In the formula, L, R １ｂ ~R ４ｂ , n, p and q are as defined above), and a step (21b) of converting compound (21b) into a sulfate ester to obtain a compound represented by the following formula: (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:

[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 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: ２１ｂ -CH=CH-(CR ２ｂ ２ ) ｎ - (OR ３ｂ ) ｐ - (CR ４ｂ ２ ) ｑ -L-OH (wherein, L, R ２ｂ ~R ４ｂ , n, p and q are as defined above. 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 produce a compound (30b) represented by the following formula: (In the formula, L, R ２ｂ ~R ４ｂ , R ２１ｂ , n, p and q are as defined above.), ２２ｂ ２ CuLi(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. (In the formula, L, R ２ｂ ~R ４ｂ , R ２１ｂ , R ２２ｂ , n, p and q are as defined above.), and oxidizing compound (32b) to obtain a compound represented by the following formula: (In the formula, L, R ２ｂ ~R ４ｂ , R ２１ｂ , R ２２ｂ, n, p and q are as defined above), and a step (33b) of converting compound (33b) into a sulfate ester to obtain a compound represented by the following formula: (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:

[0597] R ２１ｂ The alkyl group as R preferably does not contain a carbonyl group. ２１ｂ 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.

[0598] R ２１ｂ is preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 8 carbon atoms which may have a substituent, more preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group having 3 to 8 carbon atoms which does not contain a carbonyl group, still more preferably H, or a linear or branched alkyl group having 1 to 8 carbon atoms which does not have a substituent, and further preferably H or a methyl group (—CH ３ ) is particularly preferred, with H being most preferred.

[0599] R ２２ｂ The alkyl group as R preferably does not contain a carbonyl group. ２２ｂThe 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.

[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, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) is most preferred.

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

[0602] R ２１ｂ and R ２２ｂ Preferably, the total number of carbon atoms in each of the groups 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. Among these, peracids are preferred, and metachloroperbenzoic acid is 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 epoxidation pressure 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 0.1 to 72 hours, more preferably 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 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0623] In step (33b), the compound (32b) can be oxidized using, for example, (a) Jones reagent (CrO ３ / H ２ SO ４(b) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method using NiCl ２ (e) a method of treating with a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as Al(CH ３ ) ３ , Al[OCH(CH ３ ) ２ ] ３ and a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted with the compound in the presence of an aluminum catalyst such as (Oppenauer oxidation).

[0624] The oxidation in step (33b) can be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include 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 step (33b) is preferably −78 to 200° C., and can be appropriately selected depending on the method employed.

[0632] The pressure for oxidation in 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: １１ｂ -CH=CH-(CR ２ｂ ２ ) ｎ - (OR ３ｂ ) ｐ - (CR ４ｂ ２ ) ｑ -L-OH (wherein, 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: (In the formula, L, R ２ｂ ~R ４ｂ , R １１ｂ , n, p and q are as defined above), and a step (41b) of converting compound (41b) into a sulfate ester to obtain a compound represented by the following formula: (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:

[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, 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; ２ O ２ , MnO ２ , KMnO ４ , RuO ４ , 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 above 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 exemplified by 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), with ethyl acetate being 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. Of 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 pressure for oxidation in 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: １１ｂ -CH=CH-(CR ２ｂ ２ ) ｎ -OH (wherein, 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: １１ｂ -CH=CH-(CR ２ｂ ２ ) ｎ -Z ５１ｂ (In the formula, R ２ｂ , R １１ｂ and n is as defined above. ５１ｂ is a halogen atom.), ３ｂ -L-OH(L,R ３ｂ is as defined above.) to produce an alkylene glycol represented by the following formula: １１ｂ -CH=CH-(CR ２ｂ ２ ) ｎ -O-R ３ｂ -L-OH (wherein, L, R ２ｂ , R ３ｂ , R １１ｂ and n is as defined above.), and a step (52) of obtaining a compound (52) represented by the following formula: (In the formula, L, R ２ｂ , R ３ｂ , R １１ｂ and n are as defined above.), and a step (53) of converting compound (53) into a sulfate ester to obtain a compound represented by the following formula: (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 As the fluorine atom, F, Cl, Br or I is preferred, and Br is more preferred.

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

[0657] The reaction in step (51) can be carried out in the presence of a phosphine such as triphenylphosphine, which 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. Examples of the base include sodium hydride, sodium hydroxide, and 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. ３ When the group represented by H is present (i.e., X ｂ is H), by contacting with an alkali such as sodium carbonate or ammonia, ３ H can be converted to sulfate.

[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 described.

[0680] In formula (c), R １ｃ is a linear or branched alkyl group having one or more carbon atoms, or a cyclic alkyl group having three 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. That is, CH ３The alkyl group also includes acyl groups such as an acetyl group represented by -C(=O)-. 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. R 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 heterocyclic ring. ３ —C(═O)—CH ２ The group represented by - has 3 carbon atoms, and ３ -C(=O)-C ２ H ４ -C(=O)-C ２ H ４ The group represented by - has 7 carbon atoms, and CH ３ The group represented by —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, 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. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０１ｃ (In the formula, R １０１ｃ The alkyl group may be one in which 75% or less, 50% or less, or 25% or less of the hydrogen atoms bonded to carbon atoms are 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 ３ｃare independently a single bond or a divalent linking group. ２ｃ and R ３ｃ are preferably each 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. 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, 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. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０２ｃ (In the formula, R １０２ｃ 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 R 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. 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 the formula, A ｃ Ha, -COOX ｃ or -SO ３ X ｃ (X ｃ represents H, a metal atom, NR ４ｃ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ４ｃ are H or organic groups, and may be the same or different. ４ｃ 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 ｃ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ４ｃ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ｃ NH ４ In this case, 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 compound, the compound of the formula: (In the formula, n １１ｃ is an integer from 0 to 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 from 2 to 10, R １２ｃmay be the same or different.) is more preferred.

[0689] n １１ｃ 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.

[0690] R １１ｃ The alkyl group as R preferably does not contain a carbonyl group. １１ｃ In the alkyl group as defined 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. Examples of the monovalent organic group containing an ester bond include a group represented by the formula: —O—C(═O)—R １０３ｃ (In the formula, R １０３ｃ is an alkyl group). １１ｃ The alkyl group as above may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated 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. １２ｃ The alkylene group as R may be linear or branched. １２ｃ The alkylene group as R preferably does not contain a carbonyl group. １２ｃ Examples of the alkyl group include an ethylene group (-C ２ H ４ -) or propylene group (-C ３ H ６ -) is more preferred. １２ｃIn the alkylene group represented by the formula: １０４ｃ (In the formula, R １０４ｃ is an alkyl group). １２ｃ The alkylene group as the above may have 75% or less of the hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of the hydrogen atoms substituted with halogen atoms, or 25% or less of the hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group that does not contain halogen atoms such as fluorine atoms or chlorine atoms.

[0692] R ２ｃ and R ３ｃ is 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 ２ H ４ -) or propylene group (-C ３ H ６ -) is more preferred.

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

[0694]

[0695]

[0696]

[0697]

[0698]

[0699]

[0700]

[0701]

[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: (In the formula, R ３ｃ As mentioned above, E ｃ is a leaving group.) and a compound (10c) represented by the formula: R ２０１ｃ ３ Si-Cl (wherein R ２０１ｃ are independently an alkyl group or an aryl group. (In the formula, R ３ｃ , R ２０１ｃ and E ｃ is as described above.), and reacting compound (11c) with a compound of the formula: (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: (In the formula, R １ｃ , R ２１ｃ , R ３ｃ and E ｃ is as described above.), and a step (12c) of obtaining a compound (12c) represented by the formula: (In the formula, R １ｃ , R ２１ｃ and R ３ｃ is as described above.), and a step (13c) of oxidizing compound (13c) to obtain a compound of the formula: (In the formula, R １ｃ , R ２１ｃ and R ３ｃ is as described above.) to obtain a compound (14c) represented by the formula (14c).

[0704] 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.

[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 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.

[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: 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 −78 to 100° C., more preferably 10 to 40° C. The temperature for the reaction of the siloxylithium compound with compound (10c) in step (11c) is preferably −100 to 0° C., more preferably −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 compound (10c) in 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 and compound (10c) in 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 products.

[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 cesium fluoride, potassium fluoride, or lithium fluoroborate (LiBF ４ ), a method using an inorganic salt such as 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, a disodium hydrogen phosphate solution can be used.

[0731] Compound (14c) may be brought into contact 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: (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: (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: (In the formula, R １ｃ , R ３ｃ and E ｃ As mentioned above, R ２４ｃ is a single bond or a divalent linking group.), and a step (21c) of obtaining a compound (21c) represented by the formula: (In the formula, R １ｃ , R ２４ｃ and R ３ｃ is as described above.), and a step (22c) of oxidizing compound (22c) to obtain a compound of the formula: (In the formula, R １ｃ , R ２４ｃ and R ３ｃ is as described above.) to obtain a compound (23c) represented by the formula (23c).

[0734] 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.

[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 R is preferably a linear or branched alkyl group having one or more carbon atoms, and more preferably a methyl group. ２３ｃ R is preferably a linear or branched alkyl group having one or more carbon atoms, and more preferably a methyl group. ２４ｃ As the alkyl group, a linear or branched alkylene group having one or more carbon atoms is preferred, and a methylene group (—CH ２ -) 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 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 cesium fluoride, potassium fluoride, or lithium fluoroborate (LiBF ４), a method using an inorganic salt such as 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 brought into contact 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 -CH ２ -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 represented by the formula: (In the formula, R １ｃ is as described above.) to form a compound represented by the formula: (In the formula, R １ｃ , R ３ｃ and E ｃ is as described above.), and oxidizing compound (31c) to obtain a compound represented by the formula (In the formula, R １ｃ , R ３ｃ and E ｃ is as described above.), and a step (32c) of obtaining a compound (32c) represented by the formula: (In the formula, R １ｃ and R ３ｃ is as described above.), and a step (33c) of oxidizing compound (33c) to obtain a compound of the formula: (In the formula, R １ｃ and R ３ｃ is as described above.) to obtain a compound (34c) represented by the formula (34c).

[0756] 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.

[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 the 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 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 (CF ３ CO ２ ) ３ ]・H ２ O (wherein, Cn ＊ represents 1,4,7-trimethyl-1,4,7-triazabicyclononane) to (NH ４ ) ２ Ce(NO ３ ) ６ and trifluoroacetic acid followed by the addition of sodium perchlorate to form a complex in a nitrile solvent.

[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 cesium fluoride, potassium fluoride, or lithium fluoroborate (LiBF ４ ), a method using an inorganic salt such as 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 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 brought into contact 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 obtained compound may be increased by removing the solvent, or by carrying out distillation, purification, etc.

[0778] The surfactant (c) may also be a compound represented by the formula: and a divinyl ketone represented by the formula: and 2-methylfuran represented by the formula: a step (51c) of obtaining a compound (51c) represented by the formula: with a furan represented by the formula: and a step (52c) of obtaining a compound (52c) represented by the formula: and oxidizing compound (53c) to obtain a compound (53c) of the formula: The compound (54c) can be suitably produced by a production method comprising 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 moles, more preferably 0.1 to 1 mole, per mole 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 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 moles, more preferably 0.1 to 1 mole, per mole 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 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 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 brought into contact 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: (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: (In the formula, Y ６１ｃ is an alkyl ester group.) to form a compound represented by the formula: (In the formula, R １ｃ , R ２１ｃ and Y６１ｃ is as described above.), and a step (61c) of reacting compound (61c) with an alkali and then with an acid to obtain a compound represented by the formula: (In the formula, R １ｃ and R ２１ｃ is as described above.) to obtain a compound (62c) represented by the formula (62c).

[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 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 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 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 the 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 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 brought into contact 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 １ｄR 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 heterocycle, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, and an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. １ｄ 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.

[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 as the 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 the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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 １ｄAs 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 have a substituent is even more preferred, a linear or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent is even more preferred, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred, and a methyl group (—CH ３ ) 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 the alkyl group preferably does not contain a carbonyl group. The alkyl group may have 75% or less of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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 ４ｄThe 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, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and a methyl group (—CH ３ ) or an ethyl group (-C ２ H ５ ) is particularly preferred.

[0831] R ２ｄ and R ４ｄ are each independently preferably H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a straight-chain or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and ３ ) or an ethyl group (-C ２ H ５ ) is even more preferred, with H being especially preferred.

[0832] In formula (d), R ３ｄ 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 of the hydrogen atoms bonded to the carbon atoms substituted with halogen atoms, 50% or less, or 25% or less, 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, and more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not have a substituent, and a methylene group (—CH ２ -), ethylene group (-C ２ H ４ -), isopropylene group (-CH(CH ３ ) CH ２ -) or propylene group (-C ３ H ６ -) is more preferred.

[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, and more preferably 0 or 1. q is preferably an integer of 0 to 10, and 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 is -SO ３ X ｄ or -COOX ｄ (X ｄ represents H, a metal atom, NR ５ｄ ４, optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and 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 X may be as defined above. ｄ is H, an alkali metal (group 1), an alkaline earth metal (group 2), or NR ５ｄ ４ is preferred, and H, Na, K, Li or NH ４ is more preferred, and Na, K or NH ４ is more preferred, Na or NH ４ is particularly preferred, and NH ４ is most preferred. ｄ NH ４ In this case, 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 represents a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), 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. ６ｄis 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 H-NMR spectrum, it is preferable that the integral value of all peak intensities observed in the chemical shift region of 2.0 to 5.0 ppm is 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, with the concentration of heavy water being 4.79 ppm.

[0846] Examples of the surfactant (d) include CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH２ CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ COONa, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ COONa, CH ３ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ CH ２ COONa, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ CH ２ COONa, CH ３ CH ２ CH ２CH ２ CH ２ CH ２ CH ２ C(O)CH ２ CH ２ COONa, CH ３ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OCH ２ CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ NHC(O)CH ２ COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２CH ２ CH ２ CH ２ CH ２ OC(O)CH ２ COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COOH、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COOLi、 CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COONH ４ CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)COONa, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(CH) ３ ) ２COOK, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, (CH ３ ) ３ CC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, (CH ３ ) ２ CHC(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, (CH ２ ) ５ CHC(O)CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ SO ３ Na, CH ３ C(O)CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OCH ２ CH ２ CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)NHCH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ NHC(O)CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(O)OCH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ OC(O)CH ２ SO ３ Na, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ H, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ K, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ Li, CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ SO ３ NH ４ CH ３ C(O)CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ C(CH) ３ ) ２SO ３ Na and the like.

[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: (In the formula, R １ｄ , R ２ｄ and n are as defined above.) and a compound (10d) represented by the following formula: (In the formula, R ３ｄ is as defined above. L is a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), 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 -S(=O) in the formula. ２ (referring to the side bonded to -), to form a sultone represented by the following formula: (In the formula, R １ｄ ~R ３ｄ , n and X ｄ is as defined above. L is a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), 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 -OSO ３ X ｄThe compound (11d) can be suitably produced by a production method including a step (11d) of obtaining a compound (11d) represented by the 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, and more preferably an aprotic polar solvent. Examples of the organic solvent include ethers, aromatic compounds, nitriles, and halogenated hydrocarbons. Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, and diethylene glycol diethyl ether, with diethyl ether and tetrahydrofuran being 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, with acetonitrile being 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 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: (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- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), 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 -CH ２ (referring to the side bonded to —OH) to obtain a compound (20d) represented by the following formula: (In the formula, R １ｄ ~R ４ｄ , n, p, q and X ｄ is as defined above. L is a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), 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 -CH ２ -COOX ｄ The compound (21d) can be suitably produced by a production method including a step (21d) of obtaining a compound (21d) represented by the 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 pressure for oxidation in 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: １１ｄ -CH=CH-Y １ｄ -OH (wherein, R １１ｄ represents 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. １ｄ is -(CR ２ｄ ２ ) ｎ -or- (CR ２ｄ ２ ) ｎ - (OR ３ｄ ) ｐ - (CR ４ｄ ２ ) ｑ -L-CH ２ - (R ２ｄ ~R ４ｄ , n, L, p and q are as defined above. L is a single bond, —CO ２ -B-*, -OCO-B-*, -CONR ６ｄ -B-*, -NR ６ｄ CO-B-* or -CO- (where -CO ２ -B-, -OCO-B-, -CONR ６ｄ -B-, -NR ６ｄ (excluding the carbonyl group contained in CO—B—), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R６ｄ is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent. * represents -CH ２ ) is hydroxylated to give a compound (100d) represented by the following formula: (In the formula, R １１ｄ and Y １ｄ is as described above.), and a step (101d) of oxidizing the compound (101d) to obtain a compound represented by the following formula: (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:

[0863] R １１ｄ The alkyl group as R preferably does not contain a carbonyl group. １１ｄ 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.

[0864] R １１ｄ is preferably H, 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, more preferably H, 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, still more preferably H, or a linear or branched alkyl group having 1 to 9 carbon atoms which does not have a substituent, and ３ ) or an ethyl group (-C ２ H ５ ) is even more preferred, H or a methyl group (—CH ３ ) is particularly preferred, with H being most preferred.

[0865] The hydroxylation in step (101d) can be carried out, for example, by (1d) reacting compound (100d) with phthalocyanine iron (II) (Fe(Pc)) and sodium borohydride in an oxygen atmosphere, or (2d) reacting compound (100d) with isopinocampheylborane (IpcBH ２ ) 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 process (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. The solvent is 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 from 0.1 to 72 hours, more preferably from 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. The solvent is 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 0.1 to 72 hours, more preferably 0.1 to 48 hours.

[0885] The oxidation in the process (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 the step (102d), the compound (101d) can be oxidized using, for example, (a) Jones reagent (CrO ３ / H ２ SO ４ (d) a method using Dess-Martin periodinane (DMP) (Dess-Martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) a method using NiCl ２ (e) a method of treating with a bleaching agent (a 5-6% aqueous solution of NaOCl) in the presence of a nickel compound such as Al(CH ３ ) ３ , Al[OCH(CH ３ ) ２ ] ３and a method in which a hydrogen acceptor such as an aldehyde or ketone is reacted with the compound in the presence of an aluminum catalyst such as (Oppenauer oxidation).

[0891] The oxidation in step (102d) can be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include 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 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: (In the formula, R １ｄ and Y １ｄ is as above. １０１ｄ is an organic group.) is decomposed by ozonolysis to obtain a compound (200d) represented by the following formula: (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:

[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 the step (201d) can be carried out by reacting the 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. The solvent is preferably water or an organic solvent, and examples thereof include water, alcohols, 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 step (201d) is preferably from -78 to 200°C, more preferably from 0 to 150°C.

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

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

[0914] Compound (10d) and compound (20d) can also be represented by the following formula: ２１ｄ -CH=CH-Y １ｄ -OH (wherein, Y １ｄ is as above. 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: (In the formula, R ２１ｄ and Y １ｄ is as described above.), and ２２ｄ ２ CuLi(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. (In the formula, R２１ｄ , R ２２ｄ and Y １ｄ is as described above.), and a step (302d) of oxidizing compound (302d) to obtain a compound represented by the following formula: (In the formula, R ２１ｄ , R ２２ｄ and Y １ｄ can be produced by a production method including a step (303d) of obtaining a compound (303d) represented by the formula:

[0915] R ２１ｄ The alkyl group as R preferably does not contain a carbonyl group. ２１ｄ 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.

[0916] R ２１ｄ is preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 8 carbon atoms which may have a substituent, more preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group having 3 to 8 carbon atoms which does not contain a carbonyl group, still more preferably H, or a linear or branched alkyl group having 1 to 8 carbon atoms which does not have a substituent, and further preferably H or a methyl group (—CH ３ ) is particularly preferred, with H being most preferred.

[0917] R ２２ｄ The alkyl group as R preferably does not contain a carbonyl group. ２２ｄThe 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.

[0918] R ２２ｄ 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 ...

Claims

1. A method for producing a purified aqueous polytetrafluoroethylene dispersion, comprising 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-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) ｑ M ２ (wherein n is 4 to 20. M ２ is H, metal atom, NR ５ ４ (R ５ is the same as above), optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. q 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) or (2) comprises a step of subjecting the aqueous polytetrafluoroethylene dispersion to an ion exchange treatment and / or concentration treatment.

3. A method for producing a modified polytetrafluoroethylene powder, comprising 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-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), 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.

4. A method for producing a modified polytetrafluoroethylene powder according to claim 3, wherein the step of removing or reducing the compound represented by general formula (1) or (2) includes a step of heat-treating the polytetrafluoroethylene powder obtained using a hydrocarbon surfactant at a temperature of 160°C or higher.

5. A method for producing a molded article using polytetrafluoroethylene produced using a hydrocarbon surfactant, the method comprising the step of removing or reducing the amount of a compound represented by the following general formula (1) or (2): General formula (1): (H-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), 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.

6. A method for producing modified polytetrafluoroethylene powder according to claim 5, wherein the step of removing or reducing the compound represented by general formula (1) or (2) includes a step of heat treatment at a temperature of 160°C or higher.

7. A method for producing modified polytetrafluoroethylene, comprising 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-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), 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.

8. 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-(CF ２ ) ｍ -COO) ｐ M １ (wherein m is 3 to 19, M １ represents H, a 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), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. p is 1 or 2.) General formula (2): (H-(CF ２ ) ｎ -SO ３ ) 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), 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.

9. A composition containing polytetrafluoroethylene and substantially free of a compound represented by the following general formula (3): General formula (3): (H-(CF ２ ) ８ -SO ３ ) ｑ M ２ (In the formula, 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), 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.

10. The composition according to claim 9, wherein the content of the compound represented by general formula (3) is 1000 ppb or less based on polytetrafluoroethylene.

11. The composition according to claim 9 or 10, wherein the content of the compound represented by general formula (3) is 25 ppb or less based on polytetrafluoroethylene.

12. The composition according to any one of claims 9 to 11, which contains a compound represented by the following general formula (4) 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 (4): (H-(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 are 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. The composition according to any one of claims 9 to 11, comprising at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (4'), wherein the content of the compound represented by the following general formula (4) is 1000 ppb or less relative to the polytetrafluoroethylene, and the content of the compound represented by the following general formula (4') is 1000 ppb or less relative to the polytetrafluoroethylene, and wherein the composition contains a nonionic surfactant in an amount of 1% or more per polytetrafluoroethylene. General formula (4): (H-(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 are 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. p is 1 or 2.) General formula (4'): (H-(CF ２ ) ８ -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 are 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 9 to 11, which contains 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 (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 are 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 any one of claims 9 to 11, comprising at least one of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'), wherein the content of the compound represented by the following general formula (5) is 1000 ppb or less relative to the polytetrafluoroethylene, and the content of the compound represented by the following general formula (5') is 1000 ppb or less relative to the polytetrafluoroethylene, and wherein the composition contains a nonionic surfactant in an amount of 1% / polytetrafluoroethylene or more. 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 are 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. 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 are 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.

16. The composition of any one of claims 12 to 15, which is an aqueous dispersion.

17. The composition according to any one of claims 9 to 11, containing a compound represented by the following general formula (4) in an amount of 1000 ppb or less relative to polytetrafluoroethylene. General formula (4): (H-(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 are 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.

18. The composition according to any one of claims 9 to 11, comprising at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (4'), wherein the content of the compound represented by the following general formula (4) is 1000 ppb or less relative to the polytetrafluoroethylene, and the content of the compound represented by the following general formula (4') is 1000 ppb or less relative to the polytetrafluoroethylene. General formula (4): (H-(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 are 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. p is 1 or 2.) General formula (4'): (H-(CF ２ ) ８ -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 are 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.

19. The composition according to any one of claims 9 to 11, containing a compound represented by the following general formula (5) in an amount of 1000 ppb or less relative to polytetrafluoroethylene. 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 are 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.

20. The composition according to any one of claims 9 to 11, comprising at least one of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'), wherein the content of the compound represented by the following general formula (5) is 1000 ppb or less relative to the polytetrafluoroethylene, and the content of the compound represented by the following general formula (5') is 1000 ppb or less relative to the polytetrafluoroethylene. 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 are 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. 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 are 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.

21. The composition according to any one of claims 9 to 11, containing a compound represented by the following general formula (4) in an amount of 25 ppb or less relative to polytetrafluoroethylene: General formula (4): (H-(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 are 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.

22. The composition according to any one of claims 9 to 11, comprising at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (4'), wherein the content of the compound represented by the following general formula (4) is 25 ppb or less relative to the polytetrafluoroethylene, and the content of the compound represented by the following general formula (4') is 25 ppb or less relative to the polytetrafluoroethylene. General formula (4): (H-(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 are 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. p is 1 or 2.) General formula (4'): (H-(CF ２ ) ８ -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 are 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.

23. The composition according to any one of claims 9 to 11, containing a compound represented by the following general formula (5) in an amount of 25 ppb or less relative to polytetrafluoroethylene. 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 are 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.

24. The composition according to any one of claims 9 to 11, comprising at least one of a compound represented by the following general formula (5) and a compound represented by the following general formula (5'), wherein the content of the compound represented by the following general formula (5) is 25 ppb or less relative to the polytetrafluoroethylene, and the content of the compound represented by the following general formula (5') is 25 ppb or less relative to the polytetrafluoroethylene. 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 are 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. 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 are 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.

25. The composition according to any one of claims 17 to 24, further comprising a compound represented by the following general formula (7) in an amount of 1000 ppb or less relative to the 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 are 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.

26. The composition according to any one of claims 9 to 25, wherein the polytetrafluoroethylene is obtained by polymerization using a hydrocarbon surfactant.

27. The composition according to any one of claims 17 to 26, which is in the form of a powder.

28. A molded article made from the composition of claim 27.

29. The molded article according to claim 28, which is an elongated article.