JPWO2020162512A1 - Method and composition for producing tetrafluoroethylene polymer - Google Patents

Abstract

A method for producing a tetrafluoroethylene polymer containing 40 mol% or more of a polymerization unit based on tetrafluoroethylene, wherein the step (I) of polymerizing tetrafluoroethylene in an aqueous medium in the presence of the polymer (A) is performed. Including, the polymer (A) consists of a polymer containing a polymerization unit based on at least one selected from the group consisting of vinylphosphonic acid, vinylsulfonic acid, and (meth) acrylic acid, and a salt thereof. Provided is a method for producing a tetrafluoroethylene polymer, which is characterized by being at least one selected from the group.

Description

The present disclosure relates to a method and a composition for producing a tetrafluoroethylene polymer.

When a tetrafluoroethylene polymer is produced by emulsion polymerization, a fluorine-containing anionic surfactant has been used, but in recent years, a polymerization method using a non-fluorinated surfactant has also been proposed.

Patent Document 1 describes a method for producing a polymer in an aqueous reaction medium, which comprises (a) at least one radical initiator, at least one non-fluorinated surfactant, and at least one monomer. Forming an aqueous emulsion; and (b) initiating the polymerization of the monomer: the non-fluorinated surfactant selected from the group consisting of polyvinyl phosphonic acid, polyacrylic acid, polyvinyl sulfonic acid and salts thereof. The manufacturing method to be carried out is described.

Patent Document 2 describes a method for producing a fluoropolymer, which comprises a step of polymerizing tetrafluoroethylene and vinylidene fluoride in the presence of a surfactant and an aqueous medium, wherein the surfactant is the following (A) to A production method characterized by being at least one selected from the group consisting of (F) is described.
Surfactant (A)
Formula: CX ₂ = CFCF _2- O- (CF (CF ₃ ) CF ₂ O) _n- CF (CF ₃ ) -Y
(In the formula, each X is the same or different and represents F or H. N represents an integer of 0 or 1-10, Y represents -SO ₃ M or -COOM, and M represents H, A _{fluorine-containing allyl ether compound represented by NH 4} or an alkali metal) and a fluorine-containing anionic surfactant having 7 or less carbon atoms (excluding the above-mentioned fluorine-containing allyl ether compound).
Surfactant (B)
A group consisting of linear 1-alkane sulfonic acid having 7 to 20 carbon atoms, linear 2-alkane sulfonic acid having 7 to 20 carbon atoms, linear 1,2-alkane sulfonic acid having 7 to 20 carbon atoms, and salts thereof. At least one alkane sulfonic acid selected from the above or a salt thereof Surface active agent (C)
At least one non-fluorinated surfactant surfactant (D) selected from the group consisting of polyvinyl phosphonic acid, polyacrylic acid, polyvinyl sulfonic acid and salts thereof.
Surfactant Surfactant having at least one repeating unit selected from the group consisting of −CH ₂ CH ₂ O− and −CH ₂ CH ₂ CH ₂ O− and having a number of repeating units of 2 to 100 (surfactant surfactant). E)
At least one surfactant selected from the group consisting of non-fluorinated surfactants and fluorinated surfactants having a molecular weight of less than 400, and functional fluoropoly containing a fluoropolyoxyalkylene chain and a functional group. Ether Surfactant (F)
Inactivated hydrocarbon-containing surfactant

International Publication No. 2007/018683 Japanese Unexamined Patent Publication No. 2017-0573779

The present disclosure provides a novel production method capable of producing a tetrafluoroethylene polymer.

The present disclosure is a method for producing a tetrafluoroethylene polymer containing 40 mol% or more of a polymerization unit based on tetrafluoroethylene, which is a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of the polymer (A). The polymer (A) containing (I) and containing a polymerization unit based on at least one selected from the group consisting of vinylphosphonic acid, vinylsulfonic acid, and (meth) acrylic acid, and the polymer (A). Provided is a method for producing a tetrafluoroethylene polymer, which is at least one selected from the group consisting of the salts.

The polymer (A) is preferably a polymer containing a polymerization unit based on (meth) acrylic acid or a salt thereof. Further, the polymer containing the polymerization unit based on (meth) acrylic acid preferably has a content of the polymerization unit based on (meth) acrylic acid of 50 mol% or more.

In the step (I), the amount of the polymer (A) is preferably 0.0001 to 10% by mass with respect to the aqueous medium.
The step (I) is preferably a step performed in the presence of a redox initiator. The step (I) is a step of obtaining particles containing a polymerization unit based on tetrafluoroethylene, and the production method of the present disclosure further comprises tetrafluoroethylene in an aqueous medium containing the particles obtained in the step (I). It is preferable to include the step (II) of polymerizing.
The step (I) is preferably a step of obtaining an aqueous dispersion having a particle concentration of 20% by mass or less.
The step (II) is preferably a step performed in the presence of an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator.

The tetrafluoroethylene polymer is preferably a perfluoropolymer, more preferably polytetrafluoroethylene, and even more preferably modified polytetrafluoroethylene.

It is preferable that the step (I) or the step (II) is carried out substantially in the absence of the fluorine-containing surfactant.
The above step (I) is preferably performed in the presence of a hydrocarbon-based surfactant.
The hydrocarbon-based surfactant is preferably an ammonium carboxylic acid salt.
In the above step (I), it is preferable to add an aqueous solution containing a hydrocarbon-based surfactant and having a pH of 5.0 or higher.

The present disclosure also comprises a tetrafluoroethylene polymer containing 40 mol% or more of a tetrafluoroethylene-based polymerization unit and a polymer (A), wherein the polymer (A) is vinylphosphonic acid, vinylsulfonic acid, and the like. And a polymer containing a polymerization unit based on (meth) acrylic acid, and a composition characterized by being at least one selected from the group consisting of salts thereof.
The polymer (A) is preferably a polymer containing a polymerization unit based on (meth) acrylic acid or a salt thereof. The polymer containing the polymerization unit based on (meth) acrylic acid preferably has a content of the polymerization unit based on (meth) acrylic acid of 50 mol% or more.
In the composition of the present disclosure, the content of the polymer (A) is preferably 10% by mass or less with respect to the tetrafluoroethylene polymer.

The tetrafluoroethylene polymer is preferably a perfluoropolymer, more preferably polytetrafluoroethylene, and even more preferably modified polytetrafluoroethylene.

The composition of the present disclosure preferably has a standard specific gravity of 2.280 or less.

It is preferred that the compositions of the present disclosure are substantially free of fluorine-containing surfactants.

The compositions of the present disclosure are preferably powders.

The production method of the present disclosure is a novel method capable of producing a tetrafluoroethylene polymer.

Unless otherwise specified in the present specification, the "organic group" means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
An example of the "organic group" is
Alkyl groups, 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,
Cycloalkenyl groups, which may have one or more substituents,
A cycloalkazienyl group which may have one or more substituents,
Aryl groups, 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,
Heteroaryl groups, which may have one or more substituents,
Cyano group,
Holmil group,
RaO-,
RaCO-,
RaSO _2- ,
RaCOO-,
RaNRaCO-,
RaCONRa-,
RaOCO- and RaOSO _2-
(In these equations, Ra is independent,
Alkyl groups, 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,
Cycloalkenyl groups, which may have one or more substituents,
A cycloalkazienyl group which may have one or more substituents,
Aryl groups, 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).
Including.
As the organic group, an alkyl group which may have one or more substituents is preferable.
In the present 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, and an aliphatic oxycarbonyl group. , Aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl Group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino Group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aromatic oxy Includes amino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoyl sulfamoyl group, dialiptic oxyphosphinyl group, or diaromatic oxyphosphinyl group. ..

The aliphatic group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, or an aliphatic amino group. , Acylamino group, carbamoylamino group and the like. Examples of the aliphatic group include an alkyl group having a total carbon atom number of 1 to 8, preferably 1 to 4, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group and a carbamoylmethyl group.

The aromatic group includes, 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 and the like. You may be doing it. The aromatic group includes an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, for example, a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group. And so on.

The heterocyclic group has 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 and the like. You may. Examples of the heterocyclic group include a 5- to 6-membered heterocycle having a total carbon atom number of 2 to 12, preferably 2 to 10, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.

The acyl group includes 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 and an amino group. , It may have an aliphatic amino group, an acylamino group, a carbamoylamino group and the like. Examples of the acyl group include an acyl group having a total carbon atom number of 2 to 8, preferably 2 to 4, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group and the like, and has, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group and the like. May be. Examples of the acylamino group include an acylamino group having a total carbon atom number of 2 to 12, preferably 2 to 8 and an alkylcarbonylamino group having a total carbon atom number of 2 to 8, such as an acetylamino group, a benzoylamino group and a 2-pyridinecarbonylamino. Groups, propanoylamino groups and the like can be mentioned.

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

The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group and the like. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total carbon number of 2 to 9, preferably an unsubstituted carbamoyl group, and an alkylcarbamoyl group having a total carbon atom number of 2 to 5, for example, an N-methylcarbamoyl group. Examples thereof include N, N-dimethylcarbamoyl group and N-phenylcarbamoyl group.

The aliphatic sulfonyl group may be saturated or unsaturated, and may be a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, or an amino group. , It may have an aliphatic amino group, an acylamino group, a carbamoylamino group and the like. Examples of the aliphatic sulfonyl group include an alkylsulfonyl group having 1 to 6 total carbon atoms, preferably 1 to 4 total carbon atoms, for example, a methanesulfonyl group.

The aromatic sulfonyl group includes 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 and the like. You may be doing it. Examples of the aromatic sulfonyl group include arylsulfonyl groups having 6 to 10 total carbon atoms, for example, benzenesulfonyl groups.

The amino group may have an aliphatic group, an aromatic group, a heterocyclic group and the like.

The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group and the like. The acylamino group includes an acylamino group having a total carbon atom number of 2 to 12, preferably an acylamino group having a total carbon atom number of 2 to 8, and more preferably an alkylcarbonylamino group having a total carbon atom number of 2 to 8, for example, an acetylamino group or a benzoylamino. Examples include a group, a 2-pyridinecarbonylamino group, a propanoylamino group and the like.

The aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, or the like.

The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group and the like. The sulfamoyl group includes a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 total carbon atoms, a dialkylsulfamoyl group having 2 to 10 total carbon atoms, and an arylsulfamoyl group having 7 to 13 total carbon atoms. , Heterocyclic sulfamoyl group with total carbon atoms 2-12, more preferably sulfamoyl group, alkyl sulfamoyl group with total carbon atoms 1-7, dialkyl sulfamoyl group with total carbon atoms 3-6, total carbon An arylsulfamoyl group having 6 to 11 atoms and a heterocyclic sulfamoyl group having 2 to 10 total carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, an N, N-dimethylsulfamoyl group, and a phenylsulfamoyl. Examples include a group, a 4-pyridinesulfamoyl group and the like.

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 and the like. Examples of the aliphatic oxy group include an alkoxy group having a total carbon atom number of 1 to 8, preferably 1 to 6, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, and a methoxyethoxy group.

The aromatic amino group and the heterocyclic amino group are an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group condensed with the aryl group, an aliphatic oxycarbonyl group, and preferably the total number of carbon atoms. Aliphatic groups 1 to 4, aliphatic oxy groups having 1 to 4 total carbon atoms, halogen atoms, carbamoyl groups having 1 to 4 total carbon atoms, nitro groups, aliphatic oxycarbonyls having 2 to 4 total carbon atoms It may have a group.

The aliphatic thio group may be saturated or unsaturated, and an alkylthio group having a total carbon atom number of 1 to 8, more preferably a total carbon atom number of 1 to 6, for example, a methylthio group or an ethylthio group. , Carbamoylmethylthio group, t-butylthio group and the like.

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

Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

The method for producing a tetrafluoroethylene (hereinafter, also referred to as “TFE”) polymer of the present disclosure is a method for producing a TFE polymer containing 40 mol% or more of a polymerization unit based on TFE, and is the above-mentioned polymer (A). Includes step (I) of polymerizing TFE in an aqueous medium in the presence of.

The polymer (A) is a polymer containing a polymerization unit based on at least one selected from the group consisting of vinylphosphonic acid, vinyl sulfonic acid, and (meth) acrylic acid, and a group consisting of salts thereof. At least one selected. The production method of the present disclosure is to produce a TFE polymer containing 40 mol% or more of TFE-based polymerization units by using the above-mentioned specific polymer (A) without using a fluorine-containing surfactant. Can be done. In addition, the number of particles of the TFE polymer produced in the aqueous dispersion obtained by production can be increased. Furthermore, the amount of TFE polymer obtained can be increased.

The polymer (A) may contain any one of vinylphosphonic acid, vinylphosphonate, vinyl sulfonic acid, vinyl sulfonic acid, (meth) acrylic acid, and a polymerization unit based on (meth) acrylic acid. good.
The polymer (A) has a total content of polymerization units based on vinylphosphonic acid, vinylphosphonate, vinylsulfonic acid, vinylsulfonate, (meth) acrylic acid and (meth) acrylic acid salt. It is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, and further preferably 80 mol% or more with respect to the total polymerization unit of (A). Is even more preferable, 90 mol% or more is particularly preferable, and 100 mol% is particularly preferable. The total content of the polymerization units may be the total content of the polymerization units based on vinylphosphonic acid and vinylphosphonate, or the total content of the polymerization units based on vinyl sulfonic acid and vinyl sulfonate. It may be the total content of polymerization units based on (meth) acrylates and (meth) acrylates. Further, the polymer (A) may contain a polymerization unit based on another monomer described later.

Examples of the polymer (A) include a polymer or a salt thereof containing a polymerization unit based on vinylphosphonic acid, a polymer or a salt thereof containing a polymerization unit based on vinyl sulfonic acid, and a polymerization unit based on (meth) acrylic acid. Examples thereof include a polymer containing the above or a salt thereof.

The polymer (A) is preferably a polymer containing a polymerization unit based on (meth) acrylic acid or a salt thereof from the viewpoint of increasing the number of particles of the TFE polymer and increasing the obtained amount. The polymer containing a polymerization unit based on (meth) acrylic acid or a salt thereof contains a polymerization unit based on at least one selected from the group consisting of acrylic acid, acrylic acid salt, methacrylic acid, and methacrylic acid salt. It is a polymer or a salt thereof, and may contain a polymerization unit based on another monomer. Specifically, (1) polyacrylic acid (a homopolymer of acrylic acid) or a salt thereof, (2) polymethacrylic acid (a homopolymer of methacrylic acid) or a salt thereof, and (3) the weight of acrylic acid and methacrylic acid. Combined or salt thereof, (4) Polymer of acrylic acid and other monomers or salt thereof, (5) Polymer of methacrylic acid and other monomers or salt thereof, (6) Acrylic acid and methacrylic acid and other Examples thereof include a polymer with a monomer or a salt thereof.
The salt of the polymer may be any one in which at least one H of -COOH of the polymerization unit based on acrylic acid or methacrylic acid is substituted with a cation, and even if all H is substituted with a cation. Alternatively, only a part of H may be substituted with a cation.

Examples of the other monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, and dimethylaminoethyl acrylate. Examples thereof include acrylic acid ester; ethylene; styrene; maleic acid and the like.

The polymer containing the polymerization unit based on the (meth) acrylic acid or a salt thereof is described in the following general formula (A1):
-[CH ₂ CH (COM)]-(A1)
(Wherein, M represents, H, a metal atom, NR 7 _^4, which may imidazolium substituted, which may have an optionally substituted pyridinium or substituted phosphonium, R ⁷ is an H or an organic group, which may be the same or different. Any two of them may be bonded to each other to form a ring), and the polymerization unit represented by the above.
The following general formula (A2):
-[CH ₂ C (CH ₃ ) (COM)]-(A2)
(Wherein, M represents, H, a metal atom, NR 7 _^4, which may imidazolium substituted, which may have an optionally substituted pyridinium or substituted phosphonium, R ⁷ is an H or an organic group and may be the same or different. Any two of them may be bonded to each other to form a ring.) It is selected from the group consisting of the polymerization units represented by. It preferably contains at least one polymerization unit.
As R ⁷ , an alkyl group is preferable. As the ^{R 7,} preferably an organic group of H or _{C 1-10,} more preferably an organic group of H or _{C 1-4,} alkyl group of H or _{C 1-4} is more preferred.
Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable.
The polymer containing the polymerization unit based on the (meth) acrylic acid or a salt thereof is selected from the group consisting of the polymerization unit represented by the general formula (A1) and the polymerization unit represented by the general formula (A2). It contains at least one polymerization unit, and may further contain a polymerization unit based on the above other monomers.

The polymer containing the polymerization unit based on the (meth) acrylic acid or a salt thereof preferably has a content of the polymerization unit based on the (meth) acrylic acid and the salt thereof in an amount of 50 mol% or more. The content of the polymerization unit based on (meth) acrylic acid and its salt is more preferably 60 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more. , 100 mol% is particularly preferred.

The number average molecular weight of the polymer (A) ^{is preferably 0.1 × 10 4} or more, more preferably 0.2 × 10 ⁴ or more, further preferably 0.3 × 10 ⁴ or more, and 0.4 × 10 ^{4 or more.} above it is particularly preferred, preferably to especially is 0.5 × 10 ⁴ or more. Further, 1.0 × 10 ⁸ or less is preferable, 5.0 × 10 ⁷ or less is more preferable, 3.0 × 10 ⁷ or less is further preferable, and 1.0 × 10 ⁷ or less is particularly preferable. If the number average molecular weight is too low, the stability of the aqueous solution may be insufficient. If the number average molecular weight is too high, the polymer (A) may be partially precipitated, precipitated or clouded or insolubilized due to storage or addition of other additives.

The weight average molecular weight of the polymer (A) ^{is preferably 0.2 × 10 4} or more, more preferably 0.4 × 10 ⁴ or more, further preferably 0.6 × 10 ⁴ or more, and 0.8 × 10 ^{4 or more.} The above is particularly preferable. Further, preferably 2.0 × 10 ⁸ or less, more preferably 1.0 × 10 ⁸ or less, more preferably 6.0 × 10 ⁷ or less, particularly preferably 2.0 × 10 ⁷ or less. If the weight average molecular weight is too low, the stability of the aqueous solution may be insufficient. If the weight average molecular weight is too high, the polymer (A) may be partially precipitated, precipitated or clouded or insolubilized due to storage or addition of other additives.

The number average molecular weight and the weight average molecular weight are values measured by using a gel permeation chromatograph GPC.
Specifically, using a gel permeation chromatograph GPC (Agilent 1260 Infinity II), a differential refractometer detector RI is used as a detector, and one TSKgei GMPWXL column and one G3000PWXL (φ7.8 mm × 30 cm, manufactured by Tosoh Corporation). ), The solvent is 0.1 M Tris (0.1 M KCl, pH 9) / acetonitrile (8/2, vol / vol), the flow velocity is 0.5 ml / min, and the column temperature is 28 ° C. The sample concentration at the time of driving is 2.0 mg / ml. Polyethylene oxide (PEO) or polyethylene glycol (PEG) is used as a standard sample. The preparation (number average molecular weight 2.0 × 10 ⁴ or more), the PEO molecular weight region, calculating the molecular weight using PEG in the low molecular weight region of a preparation (number average molecular weight of less than 2.0 × 10 ⁴⁾ Can be done.

It is preferable that the polymer (A) is water-soluble and exhibits a thickening ability showing dispersibility, chelating ability and fluidity.

The polymer (A) can be produced by a conventionally known method. Moreover, a commercially available product can be used. In particular, specific examples of the polymer (A) include Eleminor MBN-2 (manufactured by Sanyo Chemical Industries, Ltd.), Aron series (manufactured by Toagosei Co., Ltd.), and Aquaric L series (manufactured by Nippon Shokubai Co., Ltd.). , Viscort (manufactured by Showa Denko Corporation), etc. It can also be purchased from Fuji Film Wako Pure Chemical Industries, Ltd.

The production method of the present disclosure comprises the step (I) of polymerizing TFE in an aqueous medium in the presence of the polymer (A).
The polymerization temperature and the polymerization pressure in the step (I) are appropriately determined by the type of the polymer (A) used, the molecular weight of the target TFE polymer, and the reaction rate.
For example, the polymerization temperature is preferably 10 to 150 ° C. The polymerization temperature is more preferably 30 ° C. or higher, further preferably 50 ° C. or higher. Further, 120 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable.
Further, the polymerization pressure is preferably 0.05 to 10 MPaG. The polymerization pressure is more preferably 0.3 MPaG or more, further preferably 0.5 MPaG or more, still more preferably 5.0 MPaG or less, still more preferably 3.0 MPaG or less. In particular, from the viewpoint of improving the obtained amount, 1.0 MPaG or more is preferable, 1.2 MPaG or more is more preferable, 1.5 MPaG or more is further preferable, 1.8 MPaG or more is further preferable, and 2.0 MPaG or more is particularly preferable. ..

In the step (I), the lower limit of the amount of the polymer (A) used is preferably 0.0001% by mass, more preferably 0.001% by mass, still more preferably 0.01% by mass with respect to the aqueous medium. %, Especially preferably 0.1% by mass. The upper limit of the amount of the polymer (A) used is preferably 10% by mass, more preferably 5% by mass, still more preferably 3% by mass, and particularly preferably 2% by mass with respect to the aqueous medium.

The polymer (A) may be added to the reactor all at once before the start of the polymerization, may be added all at once after the start of the polymerization, or may be added in a plurality of times during the polymerization. It may be added continuously during the polymerization.

In the step (I), the amount of the polymer (A) at the start of the polymerization is preferably 1 mass ppm or more with respect to the aqueous medium. The amount of the polymer (A) at the start of polymerization is preferably 10% by mass or more, more preferably 50% by mass or more, still more preferably 100% by mass or more, still more preferably 200% by mass or more. Is. The upper limit is not particularly limited, but for example, it is preferably 100,000 mass ppm, and more preferably 50,000 mass ppm. When the amount of the polymer (A) at the start of the polymerization is in the above range, an aqueous dispersion having a smaller average primary particle size and more excellent stability can be obtained.

It can be said that the above-mentioned polymerization was started when TFE or the like in the reactor became a polymer and the pressure drop in the reactor occurred. US Pat. No. 3,391,099 contains two separate stages of the polymerization process, first the formation of polymer nuclei as nucleation sites, and then the polymerization of established particles. Dispersion polymerization of tetrafluoroethylene in an aqueous medium consisting of growth stages is disclosed. The polymerization is usually started when both the monomer to be polymerized and the polymerization initiator are filled in the reactor. In the present disclosure, the additive related to the formation of the nucleation site is referred to as a nucleation agent.

The step (I) may include a step of continuously adding the polymer (A). To continuously add the polymer (A) is, for example, to add the polymer (A) not all at once, but over time, without interruption, or in divided portions. By including the above steps, an aqueous dispersion having a smaller average primary particle size and more excellent stability can be obtained.

The production method of the present disclosure can be efficiently carried out by using at least one of the above polymers (A). Further, the step (I) may be produced by using two or more of the polymers (A) at the same time, or may remain in a volatile one or a molded product made of the TFE polymer. If it is, a surfactant may be used at the same time. As the surfactant, a hydrocarbon-based surfactant described later can be used.

In the step (I), an aqueous medium, the polymer (A), TFE, and if necessary, a monomer other than TFE, other additives, and the like are charged into the polymerization reactor, and the contents of the reactor are charged. It can be carried out by stirring and keeping the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of a polymerization initiator to initiate the polymerization reaction. After the start of the polymerization reaction, TFE, a monomer other than TFE, a polymerization initiator, a chain transfer agent, the above-mentioned surfactant and the like may be additionally added depending on the purpose. The polymer (A) may be added after the polymerization reaction has started.

The polymerization initiator is not particularly limited as long as it can generate radicals in the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Further, the polymerization can be started as a redox in combination with a reducing agent or the like. The concentration of the polymerization initiator is appropriately determined depending on the type of the monomer, the molecular weight of the target TFE polymer, and the reaction rate.

As the polymerization initiator, an oil-soluble radical polymerization initiator, a water-soluble radical polymerization initiator or a redox initiator can be used.

The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkylperoxycarbonates such as diisopropylperoxydicarbonate and disec-butylperoxydicarbonate, and t-butylperoxy. Peroxyesters such as isobutyrate and t-butylperoxypivalate, dialkyl peroxides such as dit-butyl peroxide, and di (ω-hydro-dodecafluorohexanoyl) peroxides and di. (Ω-Hydro-Tetradecafluoroheptanoyl) Peroxide, Di (ω-Hydro-Hexadecafluorononanoyl) Peroxide, Di (Perfluorobutyryl) Peroxide, Di (Perfluorovaleryl) Peroxide, Di (Perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω-chloro-hexafluorobutyryl) Peroxide, Di (ω-Chloro-Decafluorohexanoyl) Peroxide, Di (ω-Chloro-Tetradecafluorooctanoyl) Peroxide, ω-Hydro-Dodecafluoroheptanoyl-ω-Hydrohexadecafluorononanoyl- Peroxide, ω-chloro-hexafluorobutyryl-ω-clo-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di (dichloropentafluorobutanoyl) peroxide , Di (Trichlorooctafluorohexanoyl) peroxide, Di (Tetrachloroundecafluorooctanoyl) peroxide, Di (Pentachlorotetradecafluorodecanoyl) peroxide, Di (Undecachlorodotoria Contafluorodocosanoyl) Peroxide di [perfluoro (or fluorochloro) acyl] peroxides and the like are typical examples.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, an ammonium salt such as persulfate or percarbonate, a potassium salt, a sodium salt, a disuccinic acid peroxide, or an organic peroxide such as a diglutaric acid peroxide. Examples thereof include oxides, t-butyl permalate, and t-butyl hydroperoxide. A reducing agent such as sulfites may also be contained, and the amount used thereof may be 0.1 to 20 times that of the peroxide.

As the polymerization initiator, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent. Therefore, it is preferable that the step (I) is further performed in the presence of a redox initiator.
Examples of the oxidizing agent include persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide; alkali metal salts of permanganic acid, ammonium permanganate and permanganic acid. triacetate manganese _{(C 6 H 9 MnO 6)} ;; cerium ammonium nitrate, cerium such as cerium sulfate (IV) salts; permanganates such as alkaline earth metal salts of permanganic acid bromate, ammonium bromate, bromate Examples thereof include bromine acid such as an alkali metal salt of bromine, an alkaline earth metal salt of bromine acid, or a salt thereof. As the permanganate salt, potassium permanganate is preferable.
Examples of the reducing agent include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid and glutaric acid or salts thereof; bromic acid or salts thereof; diimine; and the like. As the dicarboxylic acid or a salt thereof, oxalic acid or a salt thereof is preferable. As the bromic acid or a salt thereof, potassium bromate is preferable.
In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt and an iron salt to the combination of the redox initiator. Examples of the copper salt include copper (II) sulfate, and examples of the iron salt include iron (II) sulfate.
As the redox initiator, the oxidizing agent is permanganate acid or a salt thereof, persulfate, manganese triacetate, cerium (IV) salt, or bromic acid or a salt thereof, and the reducing agent is dicarboxylic acid or a salt thereof. The salt or diimine is preferable.
More preferably, the oxidizing agent is permanganic acid or a salt thereof, persulfate, or bromine acid or a salt thereof, and the reducing agent is dicarboxylic acid or a salt thereof.
As the above combination, from the viewpoint of redox potential, a combination of permanganate or a salt thereof and a dicarboxylic acid or a salt thereof is more preferable, and a combination of potassium permanganate and oxalic acid is particularly preferable.

Examples of the redox initiator include potassium permanganate / oxalic acid, potassium permanganate / oxalic acid, manganese triacetate / oxalic acid, manganese triacetate / ammonium oxalate, ammonium cerium nitrate / oxalic acid, ammonium cerium nitrate /. Combinations such as ammonium oxalate are mentioned, with potassium permanganate / oxalic acid being particularly preferred.
When a redox initiator is used, either an oxidizing agent or a reducing agent may be charged in advance in the polymerization tank, and then the other may be continuously or intermittently added to initiate polymerization. For example, when potassium permanganate / oxalic acid is used, it is preferable to charge oxalic acid in the polymerization tank and continuously add potassium permanganate to the oxalic acid.
When the term "potassium permanganate / oxalic acid" is used in the redox initiator of the present specification, it means a combination of potassium permanganate and oxalic acid. The same applies to other compounds.

By using the redox initiator in the above step (I), the number of particles of the TFE polymer produced in the aqueous dispersion can be increased. In addition, the amount of TFE polymer obtained can be increased. As the redox initiator, those described above can be used.
When a redox initiator is used, the oxidizing agent and the reducing agent may be added in a batch at the initial stage of polymerization, the reducing agent may be added in a batch at the initial stage of polymerization, and the oxidizing agent may be continuously added. The oxidizing agent may be added all at once at the initial stage of polymerization, and the reducing agent may be continuously added, or both the oxidizing agent and the reducing agent may be continuously added.

The amount of the polymerization initiator added is not particularly limited, but an amount (for example, a concentration of several ppm per water) or more that does not significantly reduce the polymerization rate is collectively, sequentially, or continuously at the initial stage of the polymerization. And add it. The upper limit is a range in which the reaction temperature may be raised while removing heat from the apparatus surface with the heat of the polymerization reaction, and a more preferable upper limit is a range in which the heat of the polymerization reaction can be removed from the apparatus surface.

In the above step (I), only TFE may be polymerized, TFE may be polymerized with a fluoromonomer other than TFE, TFE may be polymerized with a fluorine-free monomer, or TFE may be polymerized. A fluoromonomer other than TFE and a fluorine-free monomer may be polymerized.

The fluoromonomer other than the above TFE may be any one that can be copolymerized with TFE, and those having at least one double bond are preferable. Examples of the fluoromonomer other than TFE include hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkylethylene, and fluoroalkylallyl. Ether, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, general formula (100): CHX ¹⁰¹ = CX ¹⁰² Rf ¹⁰¹ (in the formula, X ¹⁰¹ and X ¹⁰² are H in one direction. Yes, the other is F, and Rf ¹⁰¹ consists of a group consisting of a fluoromonomer represented by a linear or branched fluoroalkyl group having 1 to 12 carbon atoms, a fluorinated vinyl heterocyclic body, and a monomer giving a cross-linking site. It is preferably at least one selected.

Examples of the fluoroalkyl vinyl ether include, for example.
General formula (110): CF ₂ = CF-ORf ¹¹¹
(In the formula, Rf ¹¹¹ represents a perfluoroorganic group.) Fluoromonomer represented by,
General formula (120): CF ₂ = CF-OCH _2- Rf ¹²¹
(In the formula, Rf ¹²¹ is a perfluoroalkyl group having 1 to 5 carbon atoms).
General formula (130): CF ₂ = CFOCF ₂ ^{ORf 131}
(In the formula, Rf ¹³¹ is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, and 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. A fluoromonomer represented by a linear or branched perfluorooxyalkyl group).
General formula (140): CF ₂ = CFO (CF ₂ CF (Y ¹⁴¹ ) O) _m (CF ₂ ) _n F
(In the formula, Y ¹⁴¹ represents a fluorine atom or a trifluoromethyl group. M is an integer of 1 to 4. n is an integer of 1 to 4.) And a fluoromonomer.
General formula (150): CF ₂ = CF-O- (CF ₂ CFY ^151- O) _n- (CFY ¹⁵² ) _m- A ¹⁵¹
(In the formula, Y ¹⁵¹ represents a fluorine atom, a chlorine atom, a -SO ₂ F group or a perfluoroalkyl group. The perfluoroalkyl group may contain _{etheric oxygen and a -SO 2 F group.} , the .n number of ^{Y 151} represents an integer of 0 to 3, which may be different or may be the same ^{.Y 152} is .m representing a fluorine atom, a chlorine atom or a -SO ₂ F group, Represents an integer of 1-5. The m Y ¹⁵² may be the same or different. A ¹⁵¹ represents -SO ₂ X ¹⁵¹ , -COZ ¹⁵¹ or -POZ ¹⁵² Z ¹⁵³ . X ¹⁵¹ represents F, Cl, Br, I, -OR ¹⁵¹ or -NR ¹⁵² R ¹⁵³ ; Z ¹⁵¹ , Z ¹⁵² and Z ¹⁵³ represent the same or different, -NR ¹⁵⁴ R ¹⁵⁵ or -OR ¹⁵⁶ . R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent the same or different alkyl, aryl, or sulfonyl-containing groups that may contain H, ammonium, alkali metals, fluorine atoms. It is preferably at least one selected from the group consisting of fluoromonomers represented by.).

In the present specification, the above-mentioned "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoroorganic group may have ether oxygen.

Examples of the fluoromonomer represented by the general formula (110) include a fluoromonomer in which Rf ¹¹¹ is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 5.

Examples of the perfluoroorganic group in the general formula (110) include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group and the like.
Further, as the fluoromonomer represented by the general formula (110), in the above general formula (110), Rf ¹¹¹ is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf ¹¹¹ is the following formula:

(In the formula, m represents an integer of 0 or 1 to 4), and Rf ¹¹¹ is the following formula:

(In the formula, n represents an integer of 1 to 4), and the like is a group represented by.

Among the fluoromonomers represented by the general formula (110),
General formula (160): CF ₂ = CF-ORf ¹⁶¹
(In the formula, Rf ¹⁶¹ represents a perfluoroalkyl group having 1 to 10 carbon atoms.) A fluoromonomer represented by the above is preferable. Rf ¹⁶¹ is preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

The fluoroalkyl vinyl ether is preferably at least one selected from the group consisting of fluoromonomers represented by the general formulas (160), (130) and (140).

As the fluoromonomer represented by the general formula (160), at least one selected from the group consisting of perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether) is preferable. At least one selected from the group consisting of fluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether) is more preferable.

The fluoromonomer represented by the general formula (130) is selected from the group consisting of _{CF 2} = CFOCF ₂ OCF ₃ , CF ₂ = CFOCF ₂ OCF ₂ CF ₃ , and CF ₂ = CFOCF ₂ OCF ₂ CF ₂ OCF _3. It is preferable that it is at least one kind.

Examples of the fluoromonomer represented by the general formula (140) include CF _{2 = CFOCF 2} CF (CF ₃ ) O (CF ₂ ) ₃ F, CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) ₂ (CF _2). ) ₃ F and CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) ₂ (CF ₂ ) It is preferable that it is at least one selected from the group consisting of _{2 F.}

As the fluoromonomer represented by the general formula (150), CF ₂ = CFOCF ₂ CF ₂ SO ₂ F, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, CF ₂ = CFOCF ₂ CF ( CF ₂ CF ₂ SO ₂ F) OCF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (SO ₂ F) ₂ is preferably selected from the group consisting of at least one selected from the group.

As the fluoromonomer represented by the general formula (100), a fluoromonomer in which Rf ¹⁰¹ is a linear fluoroalkyl group is preferable, and a fluoromonomer in which Rf ¹⁰¹ is a linear perfluoroalkyl group is more preferable. The carbon number of Rf ¹⁰¹ is preferably 1 to 6. Examples of the fluoromonomer represented by the general formula (100) include CH _{2 = CFCF 3} , CH ₂ = CFCF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₂ H, CH. ₂ = CFCF ₂ CF ₂ CF ₂ CF ₃ , CHF = CHCF ₃ (E body), CHF = CHCF ₃ (Z body), etc. Among them, CH 2 = CFCF ₃ is _{2, 3, 3,} 3-Tetrafluoropropylene is preferred.

As fluoroalkylethylene,
General formula (170): CH ₂ = CH- (CF ₂ ) _n- X ¹⁷¹
Fluoroalkylethylene represented by (where X ¹⁷¹ is H or F and n is an integer of 3-10) is preferred, CH ₂ = CH-C ₄ F ₉ and CH ₂ = CH. More preferably, it is at least one selected from the group consisting of −C ₆ F _13.

Examples of the fluoroalkylallyl ether include
General formula (240): CF ₂ = CF-CF _2- ORf ¹¹¹
(In the formula, Rf ¹¹¹ represents a perfluoroorganic group.) Examples thereof include fluoromonomers represented by.

^{Rf 111} of the general formula (240 as a ^{.Rf 111} is the same as ^{Rf 111} of the general formula (110), perfluoro alkoxyalkyl group perfluoroalkyl group or 1 to 10 carbon atoms having 1 to 10 carbon atoms Preferred as the fluoroalkylallyl ether represented by the general formula (240), CF ₂ = CF-CF _2- O-CF ₃ , CF ₂ = CF-CF _2- OC ₂ F ₅ , CF ₂ = CF. At least one selected from the group consisting of _{−CF 2} −O−C ₃ F ₇ and CF ₂ = CF − CF ₂ −O−C ₄ F _{9 is preferable, and CF 2} = CF −CF ₂ −O− More preferably, at least one selected from the group consisting of C ₂ F ₅ , CF ₂ = CF-CF _2- OC ₃ F ₇ , and CF ₂ = CF-CF _2- OC ₄ F _9. CF ₂ = CF-CF _2- O-CF ₂ CF ₂ CF ₃ is more preferable.

（式中、Ｘ^２３１及びＸ^２３２は、独立に、Ｆ、Ｃｌ、メトキシ基又はフッ素化メトキシ基であり、Ｙ^２３１は式Ｙ^２３２又は式Ｙ^２３３である。As the fluorinated vinyl heterocyclic body, the general formula (230):

(In the formula, X ²³¹ and X ²³² are independently F, Cl, methoxy group or fluorinated methoxy group, and Y ²³¹ is the formula Y ²³² or the formula Y ²³³ .

（式中、Ｚ^２３１及びＺ^２３２は、独立に、Ｆ又は炭素数１〜３のフッ素化アルキル基である。））で表されるフッ素化ビニルヘテロ環状体が挙げられる。

(In the formula, Z ²³¹ and Z ²³² are independently F or a fluorinated alkyl group having 1 to 3 carbon atoms.)) Examples thereof include fluorinated vinyl heterocyclic bodies.

As a monomer that gives a cross-linking site,
General formula (180): CX ¹⁸¹ ₂ = CX ^182- R _f ¹⁸¹ CHR ¹⁸¹ X ¹⁸³
(In the formula, X ¹⁸¹ and X ¹⁸² are independently hydrogen atoms, fluorine atoms or CH ₃ , and R _f ¹⁸¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly). An oxyalkylene group, ^R181 is a hydrogen atom or CH ₃ , and X ¹⁸³ is a fluoromonomer represented by an iodine atom or a bromine atom.
General formula (190): CX ¹⁹¹ ₂ = CX ^192- R _f ¹⁹¹ X ¹⁹³
(In the formula, X ¹⁹¹ and X ¹⁹² are independently hydrogen atoms, fluorine atoms or CH ₃ , and R _f ¹⁹¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group. X ¹⁹³ is a fluoromonomer represented by an iodine atom or a bromine atom.
General formula (200): CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) _m (CF ₂ ) _n −X ²⁰¹
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ²⁰¹ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH ₂ I.) Fluoromonomer represented by and
General formula (210): CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _m (CF (CF ₃ )) _n −X ²¹¹
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ²¹¹ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or −CH ₂ OH). Represented fluoromonomer and
General formula (220): CR ²²¹ R ²²² = CR ²²³ -Z ²²¹ -CR ²²⁴ = CR ²²⁵ R ²²⁶
(In the formula, R ²²¹ and R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ and R ²²⁶ are the same or different, hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Z ²²¹ is a linear or branched group. An alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, and at least a partially fluorinated alkylene group having 1 to 10 carbon atoms or an oxyalkylene group which may have an oxygen atom in the form. Group or
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m (CF 2 O) n -CF 2 - (Q) p -
(In the formula, Q is an alkylene group or an oxyalkylene group. P is 0 or 1. M / n is 0.2 to 5.), And the molecular weight is 500 to 10000 (par). It is a fluoropolyoxyalkylene group. ) Is preferably at least one selected from the group consisting of the monomers.

It is preferable that X ¹⁸³ and X ^{193 are iodine atoms.} R _f ¹⁸¹ and R _f ¹⁹¹ are preferably perfluoroalkylene groups having 1 to 5 carbon atoms. ^R181 is preferably a hydrogen atom. X ²⁰¹ is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or −CH ₂ I. X ²¹¹ is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or −CH ₂ OH.

As the monomers giving the cross-linking site, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ I, CF ₂ = CFOCF ₂ CF ₂ CH ₂ I, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CN, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOH, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH, CH ₂ = CHCF ₂ CF ₂ I, CH ₂ = CH (CF ₂ ) ₂ CH = CH ₂ , CH ₂ = CH (CF ₂ ) ₆ CH = CH ₂ , and CF ₂ = CFO (CF ₂ ) ₅ It is preferably at least one selected from the group consisting of CN, and CF ₂ = CFOCF ₂ CF ( CF ₃₎ and more preferably _OCF 2 _CF 2 CN and _{CF 2 = CFOCF 2 CF 2 CH} 2 , at least one selected from the group consisting of I.

Examples of the fluorine-free monomer include hydrocarbon-based monomers having reactivity with TFE. Examples of the hydrocarbon-based monomer include alkenes such as ethylene, propylene, butylene and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether; vinyl acetate, vinyl propionate, n. -Vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versaticate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, benzoic acid Vinyl, para-t-butyl benzoate vinyl, cyclohexanecarboxylate vinyl, monoclonal vinyl acetate, adipate vinyl, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl katsura acid, vinyl undecylate, hydroxyacetic acid Vinyl esters such as vinyl, vinyl hydroxypropioate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, vinyl hydroxycyclohexanecarboxylate; ethylallyl ether, propylallyl ether, butylallyl ether, isobutylallyl ether, Alkyl allyl ethers such as cyclohexyl allyl ether; Alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester and the like can be mentioned.

The fluorine-free monomer may also be a functional group-containing hydrocarbon-based monomer (excluding the monomer that provides a cross-linking site). Examples of the functional group-containing hydrocarbon monomer include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; itaconic acid, succinic acid, anhydrous succinic acid, and fumal. Fluoro-free monomer having a carboxyl group such as acid, fumaric acid anhydride, crotonic acid, maleic acid, maleic anhydride, perfluorobutenoic acid; fluorine-free monomer having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether; aminoalkyl Fluoro-free monomers having an amino group such as vinyl ether and aminoalkylallyl ether; examples thereof include fluorine-free monomers having an amide group such as (meth) acrylamide and methylol acrylamide.

Monomers other than the above TFE may be appropriately selected according to the desired TFE polymer, and those other than those exemplified above can be used.
For example, when the TFE polymer is polytetrafluoroethylene, a modified monomer described later can be used, and a monomer contained in the melt-processable fluororesin and fluororubber described later can also be used.

In the above step (I), particles of a desired TFE polymer can be obtained by polymerizing one or more of TFE and, if necessary, a fluoromonomer other than TFE and a fluorine-free monomer. ..
The TFE polymer obtained by the production method of the present disclosure will be described in detail later.

The aqueous medium is a reaction medium for polymerizing and means a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and water and, for example, a fluorine-free organic solvent such as alcohol, ether, and a ketone, and / or a fluorine-containing organic solvent having a boiling point of 40 ° C. or lower are used. And may be included.

It is preferable that the step (I) is for polymerizing tetrafluoroethylene in the absence of a fluorine-containing surfactant.
Conventionally, a fluorine-containing surfactant has been used for the polymerization of a TFE polymer, but in the production method of the present disclosure, the polymer (A) is used without using a fluorine-containing surfactant. A TFE polymer can be obtained.
As used herein, "substantially in the absence of a fluorine-containing surfactant" means that the amount of the fluorine-containing surfactant is 10 mass ppm or less, preferably 1 mass ppm or less, with respect to an aqueous medium. It is more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and even more preferably 1 mass ppb or less.

Examples of the fluorine-containing surfactant include anionic fluorine-containing surfactants.
The anionic fluorine-containing surfactant may be, for example, a surfactant containing a fluorine atom having a total carbon number of 20 or less in a portion excluding the anionic group.

The fluorine-containing surfactant may also be a surfactant containing fluorine having an anionic moiety having a molecular weight of 1000 or less, more preferably 800 or less, still more preferably 600 or less.
The "anionic portion" means a portion of the fluorine-containing surfactant excluding the cation. For example, in the case of _{F (CF} 2) n1 COOM of formula (I) to be described later, a part of the _{"F (CF 2)} n1 COO".

Examples of the fluorine-containing surfactant include a fluorine-containing surfactant having a LogPOW of 3.5 or less. The LogPOW is the partition coefficient between 1-octanol and water, and LogP [in the formula, P is the octanol in which the octanol / water (1: 1) mixture containing the fluorine-containing interface active agent is phase-separated. Represents the fluorine-containing surfactant concentration / water-containing fluorine-containing surfactant concentration ratio].
The LogPOW is a column; TOSOH ODS-120T column (φ4.6 mm × 250 mm, manufactured by Toso Co., Ltd.), eluent; acetonitrile / 0.6% by mass HClO4 water = 1/1 (vol / vol%), flow velocity; For standard substances (heptanoic acid, octanoic acid, nonanoic acid and decanoic acid) having a known octanol / water partition coefficient under the conditions of 1.0 ml / min, sample volume; 300 μL, column temperature; 40 ° C., detection light; UV210 nm. HPLC is performed to prepare a calibration line with each elution time and a known octanol / water partition coefficient, and the calculation line is calculated from the HPLC elution time in the sample solution based on this calibration line.

Specifically, as the fluorine-containing surfactant, US Patent Application Publication No. 2007/0015864, US Patent Application Publication No. 2007/00158865, US Patent Application Publication No. 2007/0015866, US Patent Publication No. 2007/0276103, US Patent Application Publication No. 2007/0117914, US Patent Application Publication No. 2007/142541, US Patent Application Publication No. 2008/0015319, US Patent No. 3250808 Japanese Patent No. 3271341, Japanese Patent Application Laid-Open No. 2003-119204, International Publication No. 2005/042593, International Publication No. 2008/060461, International Publication No. 2007/0463777, International Publication No. 2007/1195226 No., International Publication No. 2007/046482, International Publication No. 2007/0463445, US Patent Application Publication No. 2014/0228531, International Publication No. 2013/189824, International Publication No. 2013/189826, etc. Can be mentioned.

The above-mentioned anionic fluorine-containing surfactant includes the following general formula (N ⁰ ):
X ⁿ⁰ −Rf ⁿ⁰ −Y ⁰ (N ⁰ )
(In the formula, X ⁿ⁰ is H, Cl or F. Rf ⁿ⁰ has 3 to 20 carbon atoms and is chain, branched or cyclic, with some or all H substituted by F. and an alkylene group, the alkylene group may contain one or more ether bonds may .Y ⁰ substituted portion of the H is the Cl is an anionic group.) the compound represented by Can be mentioned.
Anionic group Y ⁰ is, -COOM, _-SO 2 M, or may be a -SO ₃ M, -COOM, or may be a -SO ₃ M.
M is, H, a metal atom, NR 7 _^4, which may imidazolium substituted, a good phosphonium also have a pyridinium which may have a substituent or substituents, R ⁷ Is an H or an organic group.
Examples of the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and examples thereof include Na, K, and Li.
The R ⁷ may be an organic group of H or C _1-10 , an organic group of H or C _1-4 , or an alkyl group of H or C _1-4.
M is, H, may be a metal atom or ^NR _{7 4,} H, an alkali metal (Group 1), alkaline earth metal (Group 2) or ^NR ₇ may be _4, H, Na, K, Li or It may be NH _4.
The above Rf ⁿ⁰ may be one in which 50% or more of H is replaced with fluorine.

（式中、Ｘ^ｎ２、Ｘ^ｎ３及びＸ^ｎ４は、同一若しくは異なってもよく、Ｈ、Ｆ、又は、炭素数１〜６のエーテル結合を含んでよい直鎖状または分岐鎖状の部分または完全フッ素化されたアルキル基である。Ｒｆ^ｎ５は、炭素数１〜３のエーテル結合を含み得る直鎖状または分岐鎖状の部分または完全フッ素化されたアルキレン基であり、Ｌは連結基であり、Ｙ^０は、上記定義したものである。但し、Ｘ^ｎ２、Ｘ^ｎ３、Ｘ^ｎ４及びＲｆ^ｎ５の合計炭素数は１８以下である。）で表される化合物が挙げられる。As a compound represented by the above general formula (N ^0),
The following general formula (N ¹ ):
X ⁿ⁰ − (CF ₂ ) _m1 − Y ⁰ (N ¹ )
^{(Wherein, X n0} is H, a Cl and F, m1 is an integer of 3 to 15, ^{Y 0} is the is as defined.), The compound represented by the following general formula ^{(N 2} ):
Rf ⁿ¹ −O− (CF (CF ₃ ) CF ₂ O) _m2 CFX ⁿ¹ −Y ⁰ (N ² )
(In the formula, Rf ⁿ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, X ⁿ¹ is F or CF ₃ , and Y ⁰ is defined above. The compound represented by (), the following ^{general formula (N 3) :.}
Rf ⁿ² (CH ₂ ) _m3- (Rf ⁿ³ ) _q −Y ⁰ (N ³ )
(In the formula, Rf ⁿ² is a partially or fully fluorinated alkyl group that may contain ether bonds of 1 to 13 carbon atoms, m3 is an integer of 1-3 and Rf ⁿ³ is linear. Alternatively, it is a branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y ⁰ is the above-defined compound.), The following general formula (N ⁴ ). :
Rf ^n4- O- (CY ⁿ¹ Y ⁿ² ) _p CF _2- Y ⁰ (N ⁴ )
(In the formula, Rf ⁿ⁴ is a linear or branched chain moiety or a fully fluorinated alkyl group that may contain an ether bond having 1 to 12 carbon atoms, and Y ⁿ¹ and ^Yn2 are the same or different. , H or F, p is 0 or 1, and Y ⁰ is the compound represented by the above definition), and the general formula (N ⁵ ) :.

(In the formula, X ⁿ² , X ⁿ³ and X ⁿ⁴ may be the same or different, and may contain H, F, or an ether bond having 1 to 6 carbon atoms, which may be a linear or branched chain portion or a complete chain. A fluorinated alkyl group. Rf ⁿ⁵ is a linear or branched chain moiety or a fully fluorinated alkylene group that may contain ether bonds of 1-3 carbon atoms, where L is a linking group. , Y ⁰ are those defined above. However, ^{the total carbon number of X n2} , X ⁿ³ , X ⁿ⁴ and Rf ⁿ⁵ is 18 or less).

More specifically, the compound represented by the above general formula (N ⁰ ) is a perfluorocarboxylic acid (I) represented by the following general formula (I) and ω-H represented by the following general formula (II). Perfluorocarboxylic acid (II), perfluoropolyether carboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), the following general Perfluoroalkoxyfluorocarboxylic acid (V) represented by the formula (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ω-H represented by the following general formula (VII). Perfluorosulfonic acid (VII), perfluoroalkylalkylene sulfonic acid represented by the following general formula (VIII) (VIII), alkylalkylene carboxylic acid (IX) represented by the following general formula (IX), the following general formula ( Fluorocarboxylic acid (X) represented by the following general formula (X), alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI), compound (XII) represented by the following general formula (XII), the following general formula (XII). Examples thereof include the compound (XIII) represented by XIII).

The perfluorocarboxylic acid (I) has the following general formula (I).
F (CF ₂ ) _n1 COM (I)
(Wherein, n1 is an integer from 3 to 14, M is H, a metal atom, NR 7 _^4, which may imidazolium substituted, pyridinium which may have a substituent or have a substituent is also good phosphonium, R ⁷ is represented by an H or an organic group.).

The above ω-H perfluorocarboxylic acid (II) has the following general formula (II).
H (CF ₂ ) _n2 COM (II)
(In the formula, n2 is an integer of 4 to 15, and M is the one defined above.).

The perfluoropolyether carboxylic acid (III) has the following general formula (III).
Rf ^1- O- (CF (CF ₃ ) CF ₂ O) _n3 CF (CF ₃ ) COM (III)
(In the formula, Rf ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is the one defined above.) ..

The perfluoroalkylalkylene carboxylic acid (IV) is described in the following general formula (IV).
Rf ² (CH ₂ ) _n4 Rf ³ COM (IV)
(In the formula, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ³ is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, and n4 is a perfluoroalkylene group having 1 to 3 carbon atoms. It is an integer, and M is the one defined above.).

The alkoxyfluorocarboxylic acid (V) has the following general formula (V).
Rf ^4- O-CY ¹ Y ² CF _2- COMM (V)
(In the formula, Rf ⁴ is a linear or branched chain moiety or a fully fluorinated alkyl group that may contain an ether bond having 1 to 12 carbon atoms, and Y ¹ and Y ² are the same or different. , H or F, where M is as defined above).

The perfluoroalkyl sulfonic acid (VI) has the following general formula (VI).
F (CF ₂ ) _n5 SO ₃ M (VI)
(In the formula, n5 is an integer of 3 to 14, and M is the one defined above.).

The above ω-H perfluorosulfonic acid (VII) has the following general formula (VII).
H (CF ₂ ) _n6 SO ₃ M (VII)
(In the formula, n6 is an integer of 4 to 14, and M is the one defined above.).

The perfluoroalkylalkylene sulfonic acid (VIII) has the following general formula (VIII).
Rf ⁵ (CH ₂ ) _n7 SO ₃ M (VIII)
(In the formula, Rf ⁵ is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is the one defined above.) ..

The above alkylalkylene carboxylic acid (IX) has the following general formula (IX).
Rf ⁶ (CH ₂ ) _n8 COM (IX)
(In the formula, Rf ⁶ is a linear or branched chain moiety or a fully fluorinated alkyl group that may contain an ether bond having 1 to 13 carbon atoms, and n8 is an integer of 1 to 3. M is as defined above).

The fluorocarboxylic acid (X) has the following general formula (X).
Rf ^7- O-Rf ^8- O-CF _2- COMM (X)
(In the formula, Rf ⁷ is a linear or branched chain moiety or a fully fluorinated alkyl group that may contain ether bonds having 1 to 6 carbon atoms, and Rf ⁸ is an alkyl group having 1 to 6 carbon atoms. It is a linear or branched chain moiety or a fully fluorinated alkyl group, where M is as defined above).

The alkoxyfluorosulfonic acid (XI) has the following general formula (XI).
Rf ^9- O-CY ¹ Y ² CF _2- SO ₃ M (XI)
(In the formula, Rf ⁹ is a partially or fully fluorinated alkyl group that is linear or branched and may contain chlorine and may contain ether bonds of 1-12 carbon atoms, Y. ¹ and Y ² are the same or different, H or F, and M is as defined above).

（式中、Ｘ^１、Ｘ^２及びＸ^３は、同一若しくは異なってもよく、Ｈ、Ｆ及び炭素数１〜６のエーテル結合を含み得る直鎖状または分岐鎖状の部分または完全フッ素化されたアルキル基であり、Ｒｆ^１０は、炭素数１〜３のパーフルオロアルキレン基であり、Ｌは連結基であり、Ｙ^０はアニオン性基である。）で表されるものである。
Ｙ^０は、−ＣＯＯＭ、−ＳＯ_２Ｍ、又は、−ＳＯ_３Ｍであってよく、−ＳＯ_３Ｍ、又は、ＣＯＯＭであってよい（式中、Ｍは上記定義したものである。）。
Ｌとしては、例えば、単結合、炭素数１〜１０のエーテル結合を含みうる部分又は完全フッ素化されたアルキレン基が挙げられる。The compound (XII) has the following general formula (XII):

(In the formula, X ¹ , X ² and X ³ may be the same or different and may contain H, F and ether bonds of 1 to 6 carbon atoms in a linear or branched chain or completely fluorinated. Rf ¹⁰ is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y ⁰ is an anionic group).
Y ⁰ may be -COOM, -SO ₂ M, or -SO ₃ M, _{and may be -SO 3} M, or COM (where M is defined above).
Examples of L include a single bond, a moiety capable of containing an ether bond having 1 to 10 carbon atoms, or a completely fluorinated alkylene group.

The compound (XIII) has the following general formula (XIII):
Rf ^11- O- (CF ₂ CF (CF ₃ ) O) _n9 (CF ₂ O) _n10 CF ₂ COM (XIII)
(In the formula, Rf ¹¹ is a fluoroalkyl group having 1 to 5 carbon atoms containing chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is the above definition. It is represented by). As the compound (XIII), CF ₂ ClO (CF ₂ CF (CF ₃ ) O) _n9 (CF ₂ O) _n10 CF ₂ COONH ₄ (mixture having an average molecular weight of 750, in the formula, n9 and n10 are defined above. There is.).

Examples of the anionic fluorine-containing surfactant include a carboxylic acid-based fluorine-containing surfactant and a sulfonic acid-based fluorine-containing surfactant.

In the above step (I), TFE may be polymerized to produce a TFE polymer having a content of 40 mol% or more of polymerization units based on TFE.

The step (I) is also preferably a step of obtaining particles containing a polymerization unit based on TFE, in which case the production method of the present disclosure further comprises an aqueous medium containing the particles obtained in the step (I). It is preferable to include the step (II) of polymerizing TFE. By the above step (II), a TFE polymer having a TFE-based polymerization unit content of 40 mol% or more can be obtained.
As described above, the number of particles of the TFE polymer is increased by obtaining the particles in the step (I) and then polymerizing the tetrafluoroethylene in an aqueous medium containing the particles obtained in the step (I). It is possible to increase the amount obtained.

When the production method of the present disclosure includes the above step (II), the step (II) may be performed using the aqueous dispersion containing the particles obtained in the above step (I) as it is.
Further, the aqueous dispersion containing the particles obtained in the step (I) may be diluted or concentrated to carry out the step (II). The dilution or concentration may be carried out as it is in the reactor, or the aqueous dispersion containing the particles obtained in the step (I) may be recovered from the reactor. Therefore, the production method of the present disclosure may further include a step of recovering the aqueous dispersion containing the particles obtained in the step (I) after the step (I) and before the step (II). ..
Further, after the step (I) and before the step (II), the step of setting the temperature of the aqueous dispersion containing the particles obtained in the step (I) to less than 50 ° C, less than 30 ° C or less than 10 ° C is included. But it may be.
When the step (I) and the step (II) are continuously performed, the stirring can be stopped once after the step (I), and then the stirring can be restarted and the step (II) can be continued.
Further, when the step (I) and the step (II) are continuously performed, after the step (I), the stirring may be stopped, the pressure in the reactor may be changed, and the stirring may be restarted. Step (II) can be performed.
Further, in order to change the monomer composition ratio of the reactor, after the step (I), the pressure of the reactor is depressurized to atmospheric pressure, each monomer is charged into the reactor, and then the step (II) is continued. You may. After the step (I), the polymerization temperature can be changed and the step (II) can be continued.

When the production method of the present disclosure includes the above-mentioned step (II), it is particularly preferable to use a redox initiator in the above-mentioned step (I). The number of particles can be increased by using a redox initiator.
When the step (I) and the step (II) are continuously performed, the redox initiator is charged in the step (I) and then the polymerization initiator in the step (II) is charged to continuously produce the product. Can be done.

When the production method of the present disclosure includes the step (II), the step (I) is preferably a step of obtaining an aqueous dispersion having a particle concentration (solid content concentration) of 20.0% by mass or less. .. The solid content concentration is more preferably 15.0% by mass or less, further preferably 10.0% by mass or less, still more preferably 8.0% by mass or less, and particularly preferably 5.0% by mass. % Or less. The solid content concentration is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and 1.0. Mass% or more is particularly preferable, and 1.5% by mass or more is particularly preferable.

The particles are particles containing a polymerization unit based on TFE. The particles may contain less than 40 mol% of the polymerization units based on TFE with respect to all the polymerization units constituting the polymer contained in the particles, but 40 mol% of the polymerization units based on TFE. It is preferable to include the above. The content of the polymerization unit based on TFE is more preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, still more preferably 80 mol% or more, and 90 mol% or more. Is particularly preferable.

The particles preferably contain 60 mol% or less of polymerization units based on a monomer other than TFE with respect to all the polymerization units constituting the polymer contained in the particles. The content of the polymerization unit based on the monomer other than TFE is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further preferably 20 mol% or less, still more preferably 10 mol% or less. Especially preferable.

The particles may have the same monomer composition ratio as (I) non-melt processable fluororesin, (II) melt processable fluororesin, (III) fluororubber, etc., which will be described later.

Further, the particles are polytetrafluoroethylene having a polymerization unit based on TFE of 99.0% by mass or more and a polymerization unit based on a monomer (modified monomer) other than TFE of 1.0% by mass or less. Especially preferable. The polytetrafluoroethylene (PTFE) may be low molecular weight PTFE or high molecular weight PTFE. Low molecular weight PTFE and high molecular weight PTFE will be described later.

The average primary particle size of the particles is preferably 300 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. The average primary particle size is preferably 0.1 nm or more, more preferably 1.0 nm or more, and further preferably 3.0 nm or more.
The average primary particle size is measured by a dynamic light scattering method. Prepare a fluoropolymer aqueous dispersion adjusted to an average primary particle size of about 1.0% by mass, and use ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) at 25 ° C. for a cumulative total of 70 times. To measure. The refractive index of the solvent (water) is 1.3328, and the viscosity of the solvent (water) is 0.8878 mPa · s.

The step (II) is a step of polymerizing TFE in an aqueous medium containing the particles. The above step (II) may be carried out by polymerizing only TFE, or if it is a polymerization method capable of increasing the content of the polymerization unit based on TFE of the produced TFE polymer to 40 mol% or more, it may be referred to as TFE. , At least one selected from the group consisting of fluoromonomers other than TFE and fluorine-free monomers may be polymerized. As the fluoromonomer other than TFE and the fluorine-free monomer, the monomer described in step (I) can be appropriately used.

The aqueous medium is a reaction medium for polymerizing and means a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and water and, for example, a fluorine-free organic solvent such as alcohol, ether, and a ketone, and / or a fluorine-containing organic solvent having a boiling point of 40 ° C. or lower are used. And may be included.
The aqueous medium in the step (II) preferably contains an aqueous medium contained in the aqueous dispersion containing the particles obtained in the step (I). In addition to the aqueous medium contained in the aqueous dispersion containing the particles, another aqueous medium may be added.

The polymerization temperature and the polymerization pressure in the step (II) are appropriately determined by the type of the monomer used, the molecular weight of the target TFE polymer, and the reaction rate.
For example, the polymerization temperature is preferably 10 to 150 ° C. The polymerization temperature is more preferably 30 ° C. or higher, further preferably 50 ° C. or higher. Further, 120 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable.
Further, the polymerization pressure is preferably 0.05 to 10 MPaG. The polymerization pressure is more preferably 0.3 MPaG or more, further preferably 0.5 MPaG or more, still more preferably 5.0 MPaG or less, still more preferably 3.0 MPaG or less.
In particular, from the viewpoint of improving the obtained amount, 1.0 MPaG or more is preferable, and 2.0 MPaG or more is more preferable.

The above step (II) may be performed in the presence of the polymer (A) or in the absence of the polymer (A).

The step (I) or step (II) is preferably a step of polymerizing TFE in an aqueous medium containing the particles in the presence of a surfactant.

In the step (I) or the step (II), the amount of the surfactant is preferably 0.0001 to 15% by mass with respect to the aqueous medium. A more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If it is less than 0.0001% by mass, the dispersion force may be insufficient, and if it exceeds 15% by mass, the effect commensurate with the addition amount cannot be obtained. The amount of the surfactant added is appropriately determined depending on the type of the monomer used, the molecular weight of the target TFE polymer, and the like.
The above-mentioned surfactant may be added to the reaction vessel all at once before the start of polymerization, may be added all at once after the start of polymerization, or may be added in multiple portions during the polymerization. Alternatively, it may be added continuously during the polymerization.

It is preferable that the step (I) or the step (II) includes a step of continuously adding the surfactant. The continuous addition of the surfactant is, for example, the addition of the surfactant not all at once, but over time, without interruption or in divided portions. By including the step of continuously adding, an aqueous dispersion having a smaller average primary particle size and more excellent stability can be obtained.

In the step (I) or the step (II), the amount of the surfactant at the start of polymerization is preferably 1 mass ppb or more with respect to the aqueous medium. The amount of the surfactant at the start of polymerization is preferably 10 mass ppb or more, more preferably 50 mass ppb or more, still more preferably 100 mass ppb or more, still more preferably 200 mass ppb or more. .. The upper limit is not particularly limited, but for example, it is preferably 100,000 mass ppm, and more preferably 50,000 mass ppm. When the amount of the surfactant at the start of polymerization is in the above range, an aqueous dispersion having a smaller average primary particle size and more excellent stability can be obtained. It is also possible to make the aspect ratio of the primary particles smaller.

In the step of continuously adding the surfactant in the above step (I) or step (II), when the concentration of the TFE polymer formed in the aqueous medium is 5.0% by mass or less, the surfactant Is preferably started to be added to the aqueous medium. It is more preferable to start adding the surfactant when the concentration is 3.0% by mass or less, further preferably to start adding when the concentration is 2.0% by mass or less, and 1.5% by mass or less. It is even more preferable to start adding at a certain time, and it is particularly preferable to start adding at a time of 1.0% by mass or less. Further, it is preferable to start adding when the concentration is less than 0.60% by mass, more preferably to start adding when the concentration is 0.50% by mass or less, and it is more preferable to start adding when the concentration is 0.36% by mass or less. It is even more preferable to start adding when the amount is 0.30% by mass or less, and even more preferably to start adding when the amount is 0.20% by mass or less, and 0.10% by mass is particularly preferable. It is particularly preferred to start adding when: Further, it is preferable to start the addition at the same time as the polymerization of the step (I) or the step (II) is started. The above concentration is the concentration with respect to the total of the aqueous medium and the TFE polymer.
By including the above steps, an aqueous dispersion having a smaller average primary particle size and more excellent stability can be obtained. In addition, an aqueous dispersion having a smaller amount of uncoagulated polymer can be obtained. Furthermore, the aspect ratio of the primary particles can be made smaller.

In the step of continuously adding the surfactant, the amount of the surfactant added is preferably 0.01 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.05% by mass, a further preferable lower limit is 0.1% by mass, a more preferable upper limit is 5% by mass, and a further preferable upper limit is 1% by mass.

In step (I) or step (II), an aqueous solution containing a hydrocarbon-based surfactant may be added. The pH of the aqueous solution containing a hydrocarbon-based surfactant is preferably 5.0 or more, more preferably 6.0 or more, and 6.5 or more because the molecular weight of the obtained TFE polymer tends to be high. Is even more preferable, 7.0 or more is even more preferable, 7.5 or more is particularly preferable, and 8.0 or more is particularly preferable. The upper limit of pH is not particularly limited, but may be 12.0 or less, or may be 11.0 or less. The pH of the aqueous solution is preferably adjusted by adding aqueous ammonia to the aqueous solution containing the hydrocarbon-based surfactant.

Examples of the surfactant include a fluorine-containing surfactant, a hydrocarbon-based surfactant, and the like, but the surfactant is not limited as long as the TFE polymer can be obtained. Examples of the fluorine-containing surfactant include those exemplified in the above step (I).

The hydrocarbon-based surfactant has a hydrophilic moiety and a hydrophobic moiety on the same molecule. These may be cationic, nonionic or anionic. The hydrocarbon-based surfactant is preferably a cationic hydrocarbon-based surfactant or an anionic hydrocarbon-based surfactant, and more preferably an anionic hydrocarbon-based surfactant.

Cationic hydrocarbon-based surfactants usually have a positively charged hydrophilic moiety such as an alkylated ammonium halide such as an alkylated ammonium bromide and a hydrophobic moiety such as a long chain fatty acid.

Anionic hydrocarbon-based surfactants usually have a hydrophilic moiety such as a carboxylate, a sulfonate or a sulfate, and a hydrophobic moiety that is a long chain hydrocarbon moiety such as an alkyl.

Nonionic hydrocarbon surfactants are usually free of charged groups and have a hydrophobic moiety that is a long chain hydrocarbon. The hydrophilic moiety of the nonionic hydrocarbon surfactant contains a water-soluble functional group such as a chain of ethylene ether derived from polymerization with ethylene oxide.

Examples of nonionic hydrocarbon-based surfactants Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

Specific examples of polyoxyethylene alkyl ether: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether and the like.

Specific examples of polyoxyethylene alkyl phenyl ether: polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like.

Specific examples of polyoxyethylene alkyl ester: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate and the like.

Specific examples of sorbitan alkyl ester: polyoxyethylene sorbitan monolaurylate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and the like.

Specific examples of polyoxyethylene sorbitan alkyl ester: polyoxyethylene sorbitan monolaurylate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and the like.

Specific examples of glycerol ester: glycerol monomyristate, glycerol monostearate, glycerol monooleate and the like.

Specific examples of the above derivatives: polyoxyethylene alkylamine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate and the like.

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

Nonionic hydrocarbon-based surfactants include Dow Chemical's Triton® X series (X15, X45, X100, etc.), Tergitol® 15-S series, and Tergitol® TMN. Series (TMN-6, TMN-10, TMN-100, etc.), Tergitol® L series, BASF's Pluronic® R series (31R1, 17R2, 10R5, 25R4 (m-22, n ~) 23), T-Det series (A138), Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10) and the like.

Examples of the anionic hydrocarbon-based surfactant include Versatic (registered trademark) 10 of Resolution Performance Products, Avanel S series (S-70, S-74, etc.) manufactured by BASF.

Examples of the anionic hydrocarbon-based surfactant include R-LM (in the formula, R is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a substituent. It is a cyclic alkyl group having 3 or more carbon atoms which may have a group, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocycle or may form a ring. L _{^{is, -ArSO 3 -, -SO 3 -}} , -SO 4 -, - PO 3 - or -COO ^- a and, M is, H, a metal atom, ^NR _{7 4,} which may have a substituent imidazolium, phosphonium may have a good pyridinium or substituted group which may have a substituent, R ⁷ is H or an organic group, it may be the same or different, any 2 Tsugaotagai They may be combined to form a ring. —ArSO ₃ ⁻ is an aryl sulfonate) as well as an anionic surfactant.
_{Specifically, CH 3-} (CH ₂ ) _n- L-M (in the formula, n is an integer of 6 to 17) represented by lauric acid, lauryl sulfate (dodecyl sulfate), and the like. M is represented by (same as above). Mixtures of those in which R is an alkyl group having 12 to 16 carbon atoms and LM is a sulfate can also be used.
As the anionic hydrocarbon-based surfactant, R ⁶ (-LM) ₂ (in the formula, R ⁶ may have a substituent and is a linear or branched alkylene having 1 or more carbon atoms. It is a cyclic alkylene group having 3 or more carbon atoms which may have a group or a substituent, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring. which may be .L _{^{is, -ArSO 3 -, -SO 3 -}} , -SO 4 -, - PO 3 - or -COO ^- a and, M is, H, a metal atom, ^NR _{7 4,} have a substituent and optionally also good imidazolium, phosphonium may have a good pyridinium or substituted group which may have a substituent, R ⁷ is H or an organic group, it may be the same or different, either The two may bind to each other to form a ring. Also included are anionic surfactants represented by _{−ArSO 3} ^−).
As the anionic hydrocarbon-based surfactant, R ⁸ (-LM) ₃ (in the formula, R ⁸ may have a substituent and is a linear or branched alkyridine having 1 or more carbon atoms and having 1 or more carbon atoms. It is a cyclic alkylidine group having 3 or more carbon atoms which may have a group or a substituent, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring. which may be .L _{^{is, -ArSO 3 -, -SO 3 -}} , -SO 4 -, - PO 3 - or -COO ^- a and, M is, H, a metal atom, ^NR _{7 4,} have a substituent and optionally also good imidazolium, phosphonium may have a good pyridinium or substituted group which may have a substituent, R ⁷ is H or an organic group, it may be the same or different, either The two may bind to each other to form a ring. Also included are anionic surfactants represented by _{−ArSO 3} ^−).
As R ⁷ , H or an alkyl group is preferable, H or an alkyl group having 1 to 10 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is further preferable.

Examples of the hydrocarbon-based surfactant include a siloxane hydrocarbon-based surfactant. Examples of the siloxane hydrocarbon-based surfactant include Silicone Surfactants, R.M. M. Hill, Marcel Dekker, Inc. , ISBN: 0-8247-00104. The structure of siloxane hydrocarbon-based surfactants includes distinct hydrophobic and hydrophilic moieties. The hydrophobic moiety comprises one or more dihydrocarbylsiloxane units, where the substituents on the silicone atom are completely hydrocarbons.
These siloxane hydrocarbon-based surfactants should be considered hydrocarbon-based surfactants in the sense that they are completely substituted by hydrogen atoms when the carbon atoms of the hydrocarbyl group can be replaced by halogens such as fluorine. That is, the monovalent substituent on the carbon atom of the hydrocarbyl group is hydrogen.

The hydrophilic moieties of siloxane hydrocarbon surfactants are sulfate, sulfonate, phosphonate, phosphate ester, carboxylate, carbonate, sulfosuccinate, taurate (as free acid, salt or ester), phosphine oxide, betaine, betaine. It may contain one or more polar moieties containing ionic groups such as copolyol, quaternary ammonium salts. The ionic hydrophobic moiety can also include an ionically functionalized siloxane graft.
Examples of such a siloxane hydrocarbon-based surfactant include polydimethylsiloxane-graft- (meth) acrylate, polydimethylsiloxane-graft-polyacrylate salt, and polydimethylsiloxane grafted quaternary amine. ..
The polar portion of the hydrophilic portion of the siloxane hydrocarbon surfactant is polyethylene oxide (PEO), and a mixed polyether such as polyethylene oxide / propylene oxide polyether (PEO / PPO); monosaccharides and disaccharides; and It may contain nonionic groups formed by water-soluble heterocycles such as pyrrolidinone. The ratio of ethylene oxide to propylene oxide (EO / PO) can be varied in the mixed polyethylene oxide / propylene oxide polyether.

The hydrophilic moiety of the siloxane hydrocarbon surfactant may also include a combination of an ionic moiety and a nonionic moiety. Such moieties include, for example, ionically end-functionalized or randomly functionalized polyethers or polyols. Preferred for practicing the production method of the present disclosure is a siloxane having a nonionic moiety, i.e., a nonionic siloxane hydrocarbon-based surfactant.

The arrangement of hydrophobic and hydrophilic moieties in the structure of siloxane hydrocarbon surfactants is diblock polymer (AB), triblock polymer (ABA) (where "B" represents the siloxane moiety of the molecule), Alternatively, it may take the form of a multi-block polymer. Alternatively, the siloxane surfactant may contain a graft polymer.

The siloxane hydrocarbon surfactant is also disclosed in US Pat. No. 6,841,616.

Examples of the siloxane-based anionic hydrocarbon-based surfactant include Lubrizol Advanced Materials, Inc. ^{Examples thereof include SilSense TM} PE-100 Silicone, SilSense ^TM CA-1 Silicone and the like, which can be obtained from Consumer Specialties of Noveon (registered trademark).

Examples of the anionic hydrocarbon-based surfactant include the sulfosuccinate surfactant Lankropol (registered trademark) K8300 of Akzo Nobel Interface Chemistry LLC.
Examples of the sulfosuccinate hydrocarbon-based surfactant include sulfosuccinate diisodecyl Na salt (Clariant's Emulsogen® SB10), sulfosuccinate diisotridecyl Na salt (Cesapinia Chemicals' Polar® TR / LNA) and the like. Be done.

Hydrocarbon-based surfactants include Omniova Solutions, Inc. PolyFox® surfactants (PolyFox ^TM PF-156A, PolyFox ^TM PF-136A, etc.) are also mentioned.

The hydrocarbon-based surfactant is preferably an anionic hydrocarbon-based surfactant. As the anionic hydrocarbon-based surfactant, the above-mentioned ones can be adopted, and for example, the following anionic hydrocarbon-based surfactants can be preferably adopted.

Examples of the anionic hydrocarbon-based surfactant include the following formula (α):
R ^100- COMM (α)
^{(Wherein, R 100} is a is .M monovalent organic group containing 1 or more carbon atoms, H, a metal ^{atom, NR 101} _4, good imidazolium be substituted, substituted The compound (α) represented by (α) is a pyridinium which may have a group or a phosphonium which may have a substituent, and R ¹⁰¹ is an H or an organic group and may be the same or different. Can be mentioned. As ^{the organic group of R 101} , an alkyl group is preferable. As R ¹⁰¹ , H or an organic group having 1 to 10 carbon atoms is preferable, H or an organic group having 1 to 4 carbon atoms is more preferable, and H or an alkyl group having 1 to 4 carbon atoms is further preferable.
In terms of surface activity, the number of carbon atoms of R ¹⁰⁰ is preferably 2 or more, 3 or more is more preferable. From the viewpoint of water solubility, the number of carbon atoms of R ¹⁰⁰ is, preferably 29 or less, more preferably 23 or less.
Examples of the metal atom of M include an alkali metal (Group 1), an alkaline earth metal (Group 2), and the like, and Na, K, or Li is preferable. The M, H, a metal atom or ^{NR 101} ₄ are preferable, H, an alkali metal (Group 1), alkaline earth metal (Group 2) or ^{NR 101} _4, more preferably, H, Na, K, Li or NH ₄ Is even more preferred, Na, K or NH ₄ is even more preferred, Na or NH ₄ is particularly preferred, and NH ₄ is most preferred.

Examples of the compound (α) include R ^102- COMM (in the formula, R ¹⁰² may have a substituent and has a linear or branched alkyl group having 1 or more carbon atoms, an alkenyl group, an alkylene group or a group. It is an alkenylene group or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent, an alkenyl group, an alkylene group or an alkenylene group, and these may contain an ether bond. When the number of carbon atoms is 3 or more. May contain a monovalent or divalent heterocycle or may form a ring; M is the same as above) and also includes anionic surfactants. Specifically, those represented by CH _3- (CH ₂ ) _n- COOM (in the equation, n is an integer of 2 to 28; M is the same as above) can be mentioned.

The compound (α) may not contain a carbonyl group (excluding the carbonyl group in the carboxyl group) from the viewpoint of emulsion stability.
Examples of the hydrocarbon-containing surfactant containing no carbonyl group include the following formula (A):
R ^103- COO-M (A)
(In the formula, R ¹⁰³ is an alkyl group, an alkenyl group, an alkylene group or an alkenylene group containing 6 to 17 carbon atoms, which may contain an ether bond. M is H, a metal atom, NR. ¹⁰¹ ₄ , imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent. R ¹⁰¹ is the same or different. The compound represented by H or an organic group) is preferably exemplified.
In the above formula (A), R ¹⁰³ is preferably an alkyl group or an alkenyl group (which may contain an ether group). The alkyl group or alkenyl group in ^{R 103 may be linear or branched.} The ^{carbon number of R 103} is not limited, but is, for example, 2 to 29.

When the alkyl group is linear, ^{the carbon number of R 103} is preferably 3 to 29, more preferably 5 to 23. When the alkyl group is branched, ^{the carbon number of R 103} is preferably 5 to 35, more preferably 11 to 23.
When the alkenyl group is linear, ^{the carbon number of R 103} is preferably 2 to 29, more preferably 9 to 23. When the alkenyl group is branched, ^{the carbon number of R 103} is preferably 4 to 29, more preferably 9 to 23.

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

The compound (α) (carboxylic acid type hydrocarbon-based surfactant) may be either a carboxylic acid or a carboxylic acid salt, but a carboxylic acid salt is preferable, and an ammonium carboxylate salt is more preferable.
Examples of the compound (α) (carboxylic acid type hydrocarbon-based surfactant) include butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid and pentadecylic acid. , Palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, bacsenic acid, linoleic acid, (9,12,15) -linolenic acid, (6,9,12) linolenic acid, eleostearic acid, arachidic acid , 8,11-Eikosazienoic acid, meadic acid, arachidonic acid, behenic acid, lignoseric acid, nervonic acid, cellotic acid, montanic acid, melicic acid, crotonic acid, myristoleic acid, palmitreic acid, sapienoic acid, oleic acid, ellaic acid , Baxenoic acid, gadrain acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosazienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, meadic acid, dihomo- γ-linolenic acid, eicosatorienic acid, stearidonic acid, arachidonic acid, eikosatetraenoic acid, adrenoic acid, bosseopentaenoic acid, eikosapentaenoic acid, osbondic acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, heric acid, And these salts.
In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecic acid, palmitic acid, and salts thereof is preferable.
As the salt, the metal atom of the formula M hydrogen of the carboxyl groups mentioned above, NR 101 _^4, which may imidazolium substituted, pyridinium which may have a substituent, or a substituent Examples thereof include those which are phosphoniums which may be possessed, but the present invention is not particularly limited.
As the above-mentioned surfactant (α) (carboxylic acid type hydrocarbon-based surfactant), particles having a small average primary particle diameter can be obtained by polymerization, and a large number of particles are generated during polymerization to efficiently polypoly. Since tetrafluoroethylene can be produced, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecylic acid, palmitic acid, and salts thereof is preferable, and lauric acid and its salts are more preferable. Salts of lauric acid are particularly preferable, and sodium laurate and ammonium laurate are most preferable.

（式中、Ｒ^１〜Ｒ^５はＨ又は一価の置換基を表し、但し、Ｒ^１及びＲ^３のうち、少なくとも１つは、一般式：−Ｙ−Ｒ^６で示される基、Ｒ^２及びＲ^５のうち、少なくとも１つは、一般式：−Ｘ−Ａで示される基、又は、一般式：−Ｙ−Ｒ^６で示される基を表す。
また、Ｘは、各出現において同一又は異なって、２価の連結基、又は、結合手；
Ａは、各出現において同一又は異なって、−ＣＯＯＭ、−ＳＯ_３Ｍ又は−ＯＳＯ_３Ｍ（Ｍは、Ｈ、金属原子、ＮＲ^７ _４、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウム、Ｒ^７は、Ｈ又は有機基）；
Ｙは、各出現において同一又は異なって、−Ｓ（＝Ｏ）_２−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＲ^８−及び−ＮＲ^８ＣＯ−からなる群より選択される２価の連結基、又は、結合手、Ｒ^８はＨ又は有機基；
Ｒ^６は、各出現において同一又は異なって、カルボニル基、エステル基、アミド基及びスルホニル基からなる群より選択される少なくとも１種を炭素−炭素原子間に含んでもよい炭素数１以上のアルキル基；
を表す。
Ｒ^１〜Ｒ^５のうち、いずれか２つがお互いに結合して、環を形成してもよい。）で示される界面活性剤（以下、界面活性剤（１）ともいう）が好ましく例示される。The hydrocarbon-based surfactant includes the following general formula (1):

(In the formula, R ^{1 to} R ⁵ represent H or a monovalent substituent, except ^{that at least one of R 1} and R ^{3 is} a group represented by the general formula: -Y-R ⁶ , R ² and of ^{R 5,} at least one of the general formula: a group represented by -X-a, or the general formula: represents a group represented by ^{-Y-R 6.}
Further, X is the same or different at each appearance, and is a divalent linking group or a bond;
A is identical or different at each occurrence, -COOM, is -SO ₃ M or -OSO ₃ M (M, H, a metal atom, ^NR _{7 4,} which may imidazolium have a substituent, the optionally having pyridinium or may have a substituent group phosphonium, R ⁷ is, H, or an organic group);
Y is the same or different at each _{occurrence, -S (= O) 2 -} , - O -, - COO -, - OCO -, - CONR 8 - and 2 selected from the group consisting of ^-NR 8 CO- valent linking group, or a bond, R ⁸ is H or an organic group;
R ⁶ is an alkyl group having 1 or more carbon atoms which may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group, which is the same or different at each appearance, between carbon atoms. ;
Represents.
Any two of R ^{1 to} R ⁵ may be bonded to each other to form a ring. ) (Hereinafter, also referred to as a surfactant (1)) is preferably exemplified.

The surfactant (1) will be described.

^Wherein, R 1 to R ⁵ represents H or a monovalent substituent, provided that one of ^{R 1} and ^{R 3,} at least one of the general formula: a group represented by ^{-Y-R 6, R 2} and At ^{least one of R 5} represents a group represented by the general formula: -X-A or ^{a group represented by the general formula: -Y-R 6.} Any two of R ^{1 to} R ⁵ may be bonded to each other to form a ring.

Examples of the substituent that the above alkyl group as R ¹ may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. A hydroxy group is preferable, and a methyl group and an ethyl group are particularly preferable.

The alkyl group as R ¹ preferably does not contain a carbonyl group.
In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkyl group preferably does not have any substituents.

The R ^1, is preferably a straight chain or branched cyclic alkyl group of an alkyl group or a substituted group may C3-10 have a 1 to 10 carbon atoms which may have a substituent , A linear or branched alkyl group having 1 to 10 carbon atoms containing no carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms containing no carbonyl group is more preferable, and the number of carbon atoms having no substituent is preferable. A linear or branched alkyl group of 1 to 10 is even more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is even more preferable, and a methyl group (-CH). ₃ ) or an ethyl group (-C ₂ H ₅ ) is particularly preferable, and a methyl group (-CH ₃ ) is most preferable.

Examples of the monovalent substituent represented by the general formula: a group represented by ^{-Y-R 6,} the general formula: a group represented by -X-A, -H, a good _{C 1-20} optionally having substituent Alkyl groups, -NH ₂ , -NHR ⁹ (R ⁹ is an organic group), -OH, -COOR ⁹ (R ⁹ is an organic group) or -OR ⁹ (R ⁹ is an organic group) are preferred. The alkyl group preferably has 1 to 10 carbon atoms.

The R _^9, preferably an alkyl group of an alkyl group or a _{C 1-10} of _{C 1-10,} alkyl group of the alkyl group or _{C 1-4} of _{C 1-4} is more preferred.

In the formula, X represents a divalent linking group or bond, which is the same or different at each appearance.
When R ⁶ does not contain any of a carbonyl group, an ester group, an amide group and a sulfonyl group, X is a divalent containing at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group. It is preferable that it is a linking group of.

The _{X, -CO -, - S (} = O) 2 -, - O -, - COO -, - OCO -, - S (= O) 2 -O -, - O-S (= O) 2 - , -CONR ⁸ - or a divalent linking group containing at least one bond selected from the group consisting of ^-NR 8 _CO-, an alkylene group of _{C 1-10,} or a bond are preferable. R ⁸ represents H or an organic group.

The organic group in R ⁸ is preferably an alkyl group. As R ⁸ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, _{an alkyl group of H or C 1-4} is more preferable, and H is even more preferable.

In the formula, A, identical or different at each occurrence, -COOM, is -SO ₃ M or -OSO ₃ M (M, H, a metal atom, ^NR _{7 4,} good imidazolium be substituted , phosphonium may have a good pyridinium or substituted group which may have a substituent, R ⁷ .4 one R ⁷ is H or an organic group represents a good.) to be identical or different .. In the general formula (1), it is one of the preferable embodiments that A is −COMM.

As ^{the organic group in R 7} , an alkyl group is preferable. As R ⁷ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, and an alkyl group of _{H or C 1-4 is further preferable.}
Examples of the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2) and the like, and Na, K or Li are preferable.

The M, H, a metal atom or ^NR _{7 4} are preferable, H, an alkali metal (Group 1), alkaline earth metal (Group 2) or ^NR _{7 4,} more preferably, H, Na, K, Li or NH ₄ Is even more preferred, Na, K or NH ₄ is even more preferred, Na or NH ₄ is particularly preferred, and NH ₄ is most preferred.

Wherein, Y are the same or different at each _{occurrence, -S (= O) 2 -} , - O -, - COO -, - OCO -, - CONR 8 - , and selected from the group consisting of ^-NR 8 CO- divalent linking group, or a bond, R ⁸ represents H or an organic group.

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

The organic group in R ⁸ is preferably an alkyl group. As R ⁸ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, _{an alkyl group of H or C 1-4} is more preferable, and H is even more preferable.

In the formula, R ⁶ may contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group, which is the same or different at each appearance, and may contain at least one carbon atom between carbon atoms. Represents the alkyl group of. The carbon number of the organic groups of ^{R 6} is preferably 1 or more, preferably 20 or less, more preferably 2 to 20, more preferably 2 to 10.

When the ^{number of carbon atoms is 2 or more, the alkyl group of R 6} contains 1 or 2 or more selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms. However, these groups are not contained at both ends of the above alkyl groups. Alkyl groups mentioned R ^6, which may be substituted by 75% or less halogen atom of the hydrogen atoms bonded to carbon atoms, may be 50% or less is optionally substituted by halogen atom, 25% or less halogen atom Although it may be substituted with, a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The R ^6,
General formula: -R ¹⁰ -Group represented by -CO-R ¹¹
General formula: Group represented by ^{−R 10} −COO − R ^11,
General formula: a group represented by ^{-R 11,}
General formula: −R ¹⁰ −NR ⁸ Group represented by CO-R ^{11 or}
General formula: -R ^10- CONR ^8- R ¹¹ group,
(In the formula, R ⁸ represents H or an organic group; R ¹⁰ is an alkylene group and R ¹¹ is an alkyl group which may have a substituent).
As R ⁶ , the group represented by the general formula: −R ¹⁰ −CO—R ¹¹ is more preferable.

The organic group in R ⁸ is preferably an alkyl group. As R ⁸ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, _{an alkyl group of H or C 1-4} is more preferable, and H is even more preferable.

The ^{number of carbon atoms of the alkylene group of R 10} is preferably 1 or more, more preferably 3 or more, more preferably 20 or less, further preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The carbon number of the alkylene group of R ¹⁰ is preferably 1 to 20, more preferably 1 to 10, and even more preferably 3 to 10.

The alkyl group of R ¹¹ may have 1 to 20 carbon atoms, preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10, further preferably 1 to 8, and 1 to 6 Especially preferably, 1 to 3 are even more preferable, 1 or 2 is particularly preferable, and 1 is most preferable. Further, ^{the alkyl group of R 11} is preferably composed of only primary carbon, secondary carbon and tertiary carbon, and particularly preferably composed of only primary carbon and secondary carbon. That is, as the R ^11, a methyl group, an ethyl group, n- propyl group, an isopropyl group are preferable, especially a methyl group is most preferred.

In the general formula (1) ^{, at least one of R 2} and R ⁵ is a group represented by the general formula: -X-A, and it is also a preferable embodiment that A is -COM. be.

As the surfactant (1), a compound represented by the general formula (1-1), a compound represented by the general formula (1-2) or a compound represented by the general formula (1-3) is preferable, and the compound represented by the general formula (1-3) is preferable. The compound represented by 1-1) or the compound represented by the general formula (1-2) is more preferable.

（式中、Ｒ^３〜Ｒ^６、Ｘ、Ａ及びＹは、上記のとおり。）General formula (1-1):

(In the formula, R ^{3 to} R ⁶ , X, A and Y are as described above.)

（式中、Ｒ^４〜Ｒ^６、Ｘ、Ａ及びＹは、上記のとおり。）General formula (1-2):

^{(Wherein, R 4 ~R 6, X,} A and Y are as described above.)

（式中、Ｒ^２、Ｒ^４〜Ｒ^６、Ｘ、Ａ及びＹは、上記のとおり。）General formula (1-3):

(In the formula, R ² , R ^{4 to} R ⁶ , X, A and Y are as described above.)

General formula: As a group represented by -X-A,
-COM,
-R ¹² COM,
-SO ₃ M,
-OSO ₃ M, -R ¹² SO ₃ M,
-R ¹² OSO ₃ M,
-OCO-R ^12- 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- COMM,
-CONR ^8- R ^12- SO ₃ M,
-CONR ^8- R ^12- OSO ₃ M,
-NR ⁸ CO-R ^12- COMM,
-NR ⁸ CO-R ^12- SO ₃ M,
-NR ⁸ CO-R ^12- OSO ₃ M,
-OS (= O) _2- R ^12- COM,
-OS (= O) _2- R ^12- SO ₃ M, or -OS (= O) _2- R ^12- OSO ₃ M
(In the formula, R ⁸ and M are as described above. R ¹² is an alkylene group of C _1-10 .) Is preferable.
In ^{the alkylene group of R 12} , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be a halogen atom. Although it may be substituted with, a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

Examples of the group represented by ^{-Y-R 6,:} the general formula
General formula: -R ¹⁰ -Group represented by -CO-R ¹¹
General formula: -OCO-R ¹⁰ -Group represented by -CO-R ¹¹
General formula: -COO-R ¹⁰ -Group represented by -CO-R ^11.
General formula: -OCO-R ¹⁰ -Group represented by -COO-R ^11.
General formula: Group represented by ^{-COO-R 11,}
General formula: -NR ⁸ CO-R ¹⁰ -Group represented by -CO-R ^{11 or}
General formula: -CONR ^8- R ^10- NR ⁸ A group represented by CO-R ¹¹ (in the formula, R ⁸ , R ¹⁰ and R ¹¹ are as described above) is preferable.

In the formula, R ⁴ and R ⁵ are independently preferably H or C _1-4 alkyl groups.
In ^{the alkyl groups of R 4} and R ⁵ , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted. May be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

^{As R 3} in the general formula (1-1) _{, an alkyl group of C 1-20} which may have H or a substituent is preferable, and an alkyl group of _{C 1-20} which does not have H or a substituent is preferable. Is more preferable, and H is further preferable.
Alkyl group of the R ³ may be substituted by 75% or less halogen atom of the hydrogen atoms bonded to carbon atoms, may be 50% or less is optionally substituted by halogen atom, 25% or less halogen atom Although it may be substituted with, a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

^{As R 2} in the general formula (1-3) _{, an alkyl group of C 1-20} which may have _{H, OH or a substituent is preferable, and C 1-} which does not have H, OH or a substituent is preferable. _{The alkyl group of 20} is more preferred, and H or OH is even more preferred.
In ^{the alkyl group of R 2} , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be a halogen atom. Although it may be substituted with, a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

（式中、Ｒ^１Ａ〜Ｒ^５Ａは、Ｈ、炭素−炭素原子間にエステル基を含んでもよい１価の炭化水素基、又は、一般式：−Ｘ^Ａ−Ａで示される基である。但し、Ｒ^２Ａ及びＲ^５Ａの少なくとも１つは、一般式：−Ｘ^Ａ−Ａで示される基を表す。
Ｘ^Ａは、各出現において同一又は異なって、２価の炭化水素基、又は、結合手；
Ａは、各出現において同一又は異なって、−ＣＯＯＭ（Ｍは、Ｈ、金属原子、ＮＲ^７ _４、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウム、Ｒ^７は、Ｈ又は有機基）；
Ｒ^１Ａ〜Ｒ^５Ａのうち、いずれか２つがお互いに結合して、環を形成してもよい。）で示される界面活性剤（１−０Ａ）等も挙げられる。The hydrocarbon-based surfactant has the following formula (1-0A):

(In the formula, R ^{1A to} R ^5A are H, a monovalent hydrocarbon group which may contain an ester group between carbon atoms, or a group represented by the general formula: -X ^A- A. , R ^2A and R ^5A represent a group represented by the general formula: -X ^A-A.
X ^A is the same or different at each appearance, a divalent hydrocarbon group, or a bond;
A may be the same or different at each occurrence, -COOM (M is H, a metal atom, NR 7 _^4, which may imidazolium substituted, pyridinium which may have a substituent group or a substituted phosphonium may have a group, R ⁷ is, H, or an organic group);
Any two of R ^{1A to} R ^5A may be bonded to each other to form a ring. ), And the like, as well as the surfactant (1-0A).

In the general formula (1-0A), in R ^{1A to} R ^5A , the number of carbon atoms of the monovalent hydrocarbon group which may contain an ester group between carbon atoms is preferably 1 to 50, preferably 5 to 20. Is more preferable. Any two of R ^{1A to} R ^5A may be bonded to each other to form a ring. As the monovalent hydrocarbon group which may contain an ester group between carbon atoms, an alkyl group is preferable.
Wherein in ^{X A,} the carbon number of the divalent hydrocarbon group is preferably from 1 to 50, and more preferably from 5 to 20. Examples of the divalent hydrocarbon group include an alkylene group and an alkanediyl group, and an alkylene group is preferable.

In the general formula (1-0A), ^{any one of R 2A} and R ^5A is preferably a group represented by the above general formula: −X ^{A −A, and R 2A} is the above general formula: −X ^A −. It is more preferably the group represented by A.

In the general formula (1-0A), as a preferred ^{embodiment, R 2A} is the general formula: is ^-X A -A group represented ^{by, R 1A, R 3A, R} 4A and ^{R 5A} is H mode Is. In this case, it is preferable X ^A represents a bond or an alkylene group having 1 to 5 carbon atoms.

In the general formula (1-0A), also as a preferred ^{embodiment, R 2A} is the general formula: a group represented by ^-X A ^{-A, R 1A} and ^{R 3A} are represented by ^-Y A -R ⁶ a group, ^{Y a} is the same or different at each occurrence, -COO -, - OCO-, or a bond, ^{R 6} is identical or different at each occurrence, with one or more alkyl groups having a carbon number It is an embodiment. In this case, it is preferable that ^{R 4A} and R ^{5A are H.}

Examples of the hydrocarbon-based surfactant represented by the general formula (1-0A) include glutaric acid or a salt thereof, adipic acid or a salt thereof, pimelic acid or a salt thereof, suberic acid or a salt thereof, azelaic acid or a salt thereof. Examples thereof include salt, suberic acid or a salt thereof.
Further, the aliphatic type carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) may be a double chain 2 hydrophilic group type synthetic surfactant, for example, a Gemini type surfactant. Examples thereof include Geminisurf (Chukyo Yushi Co., Ltd.), Gemsurf α142 (12 carbon atoms lauryl group), Gemsurf α102 (10 carbon atoms), Gemsurf α182 (14 carbon atoms) and the like.

Examples of the hydrocarbon-based surfactant include hydrocarbon-based surfactants having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group).

（式中、Ｒ^１ａは、炭素数１以上の直鎖状若しくは分岐鎖状のアルキル基又は炭素数３以上の環状のアルキル基であり、炭素原子に結合した水素原子がヒドロキシ基又はエステル結合を含む１価の有機基により置換されていてもよく、炭素数が２以上の場合はカルボニル基を含んでもよく、炭素数が３以上の場合は１価又は２価の複素環を含んでも環を形成していてもよい。Ｒ^２ａ及びＲ^３ａは、独立に、単結合又は２価の連結基である。Ｒ^１ａ、Ｒ^２ａ及びＲ^３ａは、炭素数が合計で６以上である。Ｘ^ａは、Ｈ、金属原子、ＮＲ^４ａ _４、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、Ｒ^４ａはＨ又は有機基であり、同一でも異なっていてもよい。Ｒ^１ａ、Ｒ^２ａ及びＲ^３ａは、いずれか２つがお互いに結合して、環を形成してもよい。）で示される界面活性剤（ａ）、下記式（ｂ）：

（式中、Ｒ^１ｂは、置換基を有してもよい炭素数１以上の直鎖状若しくは分岐鎖状のアルキル基又は置換基を有してもよい炭素数３以上の環状のアルキル基であり、炭素数が３以上の場合は１価又は２価の複素環を含んでも環を形成していてもよい。Ｒ^２ｂ及びＲ^４ｂは、独立に、Ｈ又は置換基である。Ｒ^３ｂは、置換基を有してもよい炭素数１〜１０のアルキレン基である。ｎは、１以上の整数である。ｐ及びｑは、独立に、０以上の整数である。Ｘ^ｂは、Ｈ、金属原子、ＮＲ^５ｂ _４、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、Ｒ^５ｂはＨ又は有機基であり、同一でも異なっていてもよい。Ｒ^１ｂ、Ｒ^２ｂ、Ｒ^３ｂ及びＲ^４ｂは、いずれか２つがお互いに結合して、環を形成してもよい。Ｌは、単結合、−ＣＯ_２−Ｂ−＊、−ＯＣＯ−Ｂ−＊、−ＣＯＮＲ^６ｂ−Ｂ−＊、−ＮＲ^６ｂＣＯ−Ｂ−＊、又は、−ＣＯ−（但し、−ＣＯ_２−Ｂ−、−ＯＣＯ−Ｂ−、−ＣＯＮＲ^６ｂ−Ｂ−、−ＮＲ^６ＣＯ−Ｂ−に含まれるカルボニル基を除く。）であり、Ｂは単結合もしくは置換基を有してもよい炭素数１から１０のアルキレン基であり、Ｒ^６ｂは、Ｈ又は置換基を有していてもよい、炭素数１〜４のアルキル基である。＊は、式中の−ＯＳＯ_３Ｘ^ｂに結合する側を指す。）で示される界面活性剤（ｂ）、下記式（ｃ）：

（式中、Ｒ^１ｃは、炭素数１以上の直鎖状若しくは分岐鎖状のアルキル基又は炭素数３以上の環状のアルキル基であり、炭素原子に結合した水素原子がヒドロキシ基又はエステル結合を含む１価の有機基により置換されていてもよく、炭素数が２以上の場合はカルボニル基を含んでもよく、炭素数が３以上の場合は１価又は２価の複素環を含んでも環を形成していてもよい。Ｒ^２ｃ及びＲ^３ｃは、独立に、単結合又は２価の連結基である。Ｒ^１ｃ、Ｒ^２ｃ及びＲ^３ｃは、炭素数が合計で５以上である。Ａ^ｃは、−ＣＯＯＸ^ｃ又は−ＳＯ_３Ｘ^ｃ（Ｘ^ｃは、Ｈ、金属原子、ＮＲ^４ｃ _４、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、Ｒ^４ｃはＨ又は有機基であり、同一でも異なっていてもよい。）である。Ｒ^１ｃ、Ｒ^２ｃ及びＲ^３ｃは、いずれか２つがお互いに結合して、環を形成してもよい。）で示される界面活性剤（ｃ）、及び、下記式（ｄ）：

（式中、Ｒ^１ｄは、置換基を有してもよい炭素数１以上の直鎖状若しくは分岐鎖状のアルキル基又は置換基を有してもよい炭素数３以上の環状のアルキル基であり、炭素数が３以上の場合は１価又は２価の複素環を含んでも環を形成していてもよい。Ｒ^２ｄ及びＲ^４ｄは、独立に、Ｈ又は置換基である。Ｒ^３ｄは、置換基を有してもよい炭素数１〜１０のアルキレン基である。ｎは、１以上の整数である。ｐ及びｑは、独立に、０以上の整数である。Ａ^ｄは、−ＳＯ_３Ｘ^ｄ又は−ＣＯＯＸ^ｄ（Ｘ^ｄは、Ｈ、金属原子、ＮＲ^５ｄ _４、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、Ｒ^５ｄはＨ又は有機基であり、同一でも異なっていてもよい。）である。Ｒ^１ｄ、Ｒ^２ｄ、Ｒ^３ｄ及びＲ^４ｄは、いずれか２つがお互いに結合して、環を形成してもよい。Ｌは、単結合、−ＣＯ_２−Ｂ−＊、−ＯＣＯ−Ｂ−＊、−ＣＯＮＲ^６ｄ−Ｂ−＊、−ＮＲ^６ｄＣＯ−Ｂ−＊、又は、−ＣＯ−（但し、−ＣＯ_２−Ｂ−、−ＯＣＯ−Ｂ−、−ＣＯＮＲ^６ｄ−Ｂ−、−ＮＲ^６ｄＣＯ−Ｂ−に含まれるカルボニル基を除く。）であり、Ｂは単結合もしくは置換基を有してもよい炭素数１から１０のアルキレン基であり、Ｒ^６ｄは、Ｈ又は置換基を有していてもよい、炭素数１〜４のアルキル基である。＊は、式中のＡ^ｄに結合する側を指す。）で示される界面活性剤（ｄ）からなる群より選択される少なくとも１種がより好ましい。As the hydrocarbon-based surfactant having one or more of the above carbonyl groups (excluding the carbonyl group in the carboxyl group), the formula: RX (in the formula, R is a carbonyl group (however, in the carboxyl group). It is a fluorine-free organic group having one or more (excluding carbonyl group) and having 1 to 2000 carbon atoms, where X is -OSO ₃ X ¹ , -COOX ¹ or -SO ₃ X ¹ (X ¹ is H, metal. atoms, NR 1 _^4, which may imidazolium substituted, have a substituent a good phosphonium optionally having also good pyridinium or a substituent, R ¹ is H or an organic radical Yes, they may be the same or different. The surfactant shown in)) is preferable. The number of carbon atoms in R is preferably 500 or less, more preferably 100 or less, further preferably 50 or less, and even more preferably 30 or less.
The hydrocarbon-based surfactant includes the following formula (a):

(In the formula, R ^1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, and the hydrogen atom bonded to the carbon atom forms a hydroxy group or an ester bond. It may be substituted with a monovalent organic group contained therein, may contain a carbonyl group when the number of carbon atoms is 2 or more, and may contain a monovalent or divalent heterocyclic ring when the number of carbon atoms is 3 or more. It may be formed. R ^2a and R ^3a are independently single-bonded or divalent linking groups. R ^1a , R ^2a and R ^3a have a total of 6 or more carbon atoms. X ^a. Is H, a metal atom, NR ^4a ₄ , an imidazolium which may have a substituent, a pyridinium which may have a substituent or a phosphonium which may have a substituent, and R ^4a is It may be H or an organic group, and may be the same or different. In R ^1a , R ^2a and R ^3a , any two of them may be bonded to each other to form a ring). (A), the following formula (b):

(In the formula, R ^1b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. If the number of carbon atoms is 3 or more, a monovalent or divalent heterocycle may be contained or a ring may be formed. R ^2b and R ^4b are independently H or a substituent. R ^3b is a substituent. , An alkylene group having 1 to 10 carbon atoms which may have a substituent. N is an integer of 1 or more. P and q are independently integers of 0 or more. X ^b is H. , Metal atom, NR ^5b ₄ , imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, R ^5b is H or organic. It is a group and may be the same or different ^{. Any two of R 1b} , R ^2b , R ^3b and R ^4b may be bonded to each other to form a ring. L is a single bond, − CO ₂ -B- *, -OCO-B- *, -CONR ^6b -B- *, -NR ^6b CO-B- *, or -CO- (however, -CO ₂ -B-, -OCO-B) -, -CONR ^6b -B-, -NR ⁶ CO-B-excluding the carbonyl group contained in), where B is an alkylene group having 1 to 10 carbon atoms which may have a single bond or a substituent. ^Yes , R 6b is an alkyl group having 1 to 4 carbon atoms, which may have H or a substituent. * Indicates the side bonded to _{−OSO 3} X ^{b in the formula).} Surface active agent (b), the following formula (c):

(In the formula, R ^1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, and the hydrogen atom bonded to the carbon atom has a hydroxy group or an ester bond. It may be substituted with a monovalent organic group contained therein, may contain a carbonyl group when the number of carbon atoms is 2 or more, and may contain a monovalent or divalent heterocyclic ring when the number of carbon atoms is 3 or more. optionally form ^{.R 2c} and ^{R 3c} are independently a single bond or a divalent linking group ^{.R 1c, R 2c} and ^{R 3c} are 5 or more total carbon atoms .A ^c Is -COOX ^c or -SO ₃ X ^c (X ^c is H, metal atom, NR ^4c ₄ , imidazolium which may have a substituent, pyridinium which may have a substituent or a substituent. R ^4c is an H or an organic group and may be the same or different.) In R ^1c , R ^2c and R ^3c , any two of them are bonded to each other. The surfactant (c) represented by () and the following formula (d):

(In the formula, R ^1d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. If the number of carbon atoms is 3 or more, a monovalent or divalent heterocycle may be contained or a ring may be formed. R ^2d and R ^4d are independently H or a substituent. R ^3d is an H or a substituent. , a substituent is an alkylene group which may C1-10 .n is a is .p and q is an integer of 1 or more, independently, an integer of 0 or more .A ^d is - SO ₃ X ^d or -COOX ^d (X ^d has an H, a metal atom, NR ^5d ₄ , an imidazolium which may have a substituent, a pyridinium which may have a substituent or a substituent. It may be a phosphonium, where R ^5d is an H or an organic group and may be the same or different.) In R ^1d , R ^2d , R ^3d and R ^4d , any two of them are bonded to each other. Then, a ring may be formed. L is a single bond, -CO ₂ ^{-B- *, -OCO} -B- *, -CONR ^6d -B- *, -NR 6d CO-B- *, or. , -CO- ( _{excluding the carbonyl group contained in -CO 2} ^{-B-, -OCO} -B-, -CONR ^6d -B-, -NR 6d CO-B-), where B is a single bond. Alternatively, it is 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. at least one member selected from the group consisting of surfactant (d) represented by the point.) the side to be bonded to a ^d in the formula are more preferred.

The surfactant (a) will be described.

In the formula (a), R ^1a is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.
When the number of carbon atoms is 3 or more, the alkyl group may contain a carbonyl group (-C (= O)-) between two carbon atoms. Further, when the number of carbon atoms is 2 or more, the above-mentioned alkyl group may contain the above-mentioned carbonyl group at the end of the above-mentioned alkyl group. That is, _{an acyl group such as an acetyl group represented by CH 3-} C (= O)-is also included in the alkyl group.
Further, the alkyl group may contain a monovalent or divalent heterocycle when the number of carbon atoms is 3 or more, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. In R ^1a , a divalent heterocycle may be inserted between two carbon atoms, or the divalent heterocycle may be located at the end and bonded to −C (= O) −. A monovalent heterocycle may be located at the end of the alkyl group.

In the present specification, the "carbon number" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocyclic ring. For example, the group represented by CH _3- C (= O) -CH _2- has 3 carbon atoms, and CH _3- C (= O) -C ₂ H _4- C (= O) -C ₂ H ₄ The group represented by − has 7 carbon atoms, and the group represented by CH ₃ −C (= O) − has 2 carbon atoms.

In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond may be substituted. It is preferably not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^101a (in the formula, R ^101a is an alkyl group).
In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.

In the formula, R ^2a and R ^3a are independently single-bonded or divalent linking groups.
It is preferable that R ^2a and R ^3a are independently single-bonded or linear or branched alkylene groups having 1 or more carbon atoms or cyclic alkylene groups having 3 or more carbon atoms.
The alkylene group constituting R ^2a and R ^3a preferably does not contain a carbonyl group.

In the alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond may be substituted. It is preferably not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^102a (in the formula, R ^102a is an alkyl group).
In the alkylene group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkylene group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.

R ^1a , R ^2a and R ^3a have a total of 6 or more carbon atoms. As the total number of carbon atoms, 8 or more is preferable, 9 or more is more preferable, 10 or more is further preferable, 20 or less is more preferable, 18 or less is more preferable, and 15 or less is further preferable.
Any two of R ^1a , R ^2a and R ^3a may be bonded to each other to form a ring.

In formula (a), ^Xa has H, a metal atom, NR ^4a ₄ , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a substituent. It is a good phosphonium and ^R4a is an H or an organic group. The four ^R4a may be the same or different. As R ^4a , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable. The X ^a, H, an alkali metal (Group 1), alkaline earth metal (Group 2) or preferably ^{NR 4a} _4, since the easily soluble in water, H, Na, K, Li or NH _4, more preferably further since the easily soluble in water, Na, K or NH ₄ are more preferred, particularly preferably Na or NH ₄ is, since removal is easy, NH ₄ being the most preferred. When X ^a is NH ₄ , the solubility of the above-mentioned surfactant in an aqueous medium is excellent, and the metal component is less likely to remain in PTFE or the final product.

R ^1a includes a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group, and 1 to 10 carbonyl groups. A linear or branched alkyl group having 2 to 45 carbon atoms, a cyclic alkyl group having 3 to 45 carbon atoms including a carbonyl group, or a monovalent or divalent complex having 3 to 45 carbon atoms. A ring-containing alkyl group is preferred.

（式中、ｎ^１１ａは０〜１０の整数であり、Ｒ^１１ａは炭素数１〜５の直鎖状若しくは分岐鎖状のアルキル基又は炭素数３〜５の環状のアルキル基であり、Ｒ^１２ａは炭素数０〜３のアルキレン基である。ｎ^１１ａが２〜１０の整数である場合、Ｒ^１２ａは各々同じであっても異なっていてもよい。）で示される基がより好ましい。Further, as R ^1a , the following formula:

(In the formula, n ^11a is an integer of 0 to 10, R ^11a is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R ^12a. Is an alkylene group having 0 to 3 carbon atoms. When n ^11a is an integer of 2 to 10, R ^12a may be the same or different from each other.) Is more preferable.

As n ^11a , an integer of 0 to 5 is preferable, an integer of 0 to 3 is more preferable, and an integer of 1 to 3 is further preferable.

The alkyl group as R ^11a preferably does not contain a carbonyl group.
In ^{the above alkyl group as R 11a} , the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond. It may be, but it is preferable that it is not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^103a (in the formula, R ^103a is an alkyl group).
In ^{the above alkyl group as R 11a} , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be halogen. Although it may be substituted with an atom, it is preferably a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom.

R ^12a is an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3.
The alkylene group as R ^12a may be linear or branched.
The alkylene group as R ^12a preferably does not contain a carbonyl group. The R ^12a, an ethylene group _(-C 2 _{H 4} -) or propylene group _(-C 3 _{H 6} -) is more preferred.
In the ^{alkylene group as R 12a} , the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond. It may be, but it is preferable that it is not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^104a (in the formula, R ^104a is an alkyl group).
In ^{the above alkylene group as R 12a} , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be halogen. Although it may be substituted with an atom, it is preferably a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or a chlorine atom.

As R ^2a and R ^3a , independently, an alkylene group having 1 or more carbon atoms which does not contain a carbonyl group is preferable, an alkylene group having 1 to 3 carbon atoms which does not contain a carbonyl group is more preferable, and an ethylene group (-C ₂ H) is preferable. ₄ -) or propylene group _(-C 3 _{H 6} -) is more preferred.

Next, the surfactant (b) will be described.

In formula (b), R ^1b is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent or a cyclic alkyl having 3 or more carbon atoms which may have a substituent. It is a group.
When the number of carbon atoms is 3 or more, the alkyl group may contain a monovalent or divalent heterocycle, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. In R ^1b , a divalent heterocycle may be inserted between two carbon atoms, or the divalent heterocycle may be located at the end and bonded to −C (= O) −. A monovalent heterocycle may be located at the end of the alkyl group.

In the present specification, the "carbon number" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

Examples of the substituent that the above alkyl group as R ^1b may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. A hydroxy group is preferable, and a methyl group and an ethyl group are particularly preferable.

The alkyl group as R ^1b preferably does not contain a carbonyl group.
In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkyl group preferably does not have any substituents.

As R ^1b , 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 preferable. , A linear or branched alkyl group having 1 to 10 carbon atoms containing no carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms containing no carbonyl group is more preferable, and the number of carbon atoms having no substituent is preferable. A linear or branched alkyl group of 1 to 10 is even more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is even more preferable, and a methyl group (-CH). ₃ ) or an ethyl group (-C ₂ H ₅ ) is particularly preferable, and a methyl group (-CH ₃ ) is most preferable.

In formula (b), R ^2b and R ^4b are independently H or substituents. The plurality of R ^2b and R ^4b may be the same or different from each other.

As the substituent as R ^2b and R ^4b , 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, and a hydroxy group are preferable. Groups and ethyl groups are particularly preferred.

The alkyl groups as R ^2b and R ^4b preferably do not contain a carbonyl group. In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkyl group preferably does not have any substituents.

The above-mentioned alkyl groups as R ^2b and R ^4b include 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 preferable, a linear or branched alkyl group having 1 to 10 carbon atoms containing no carbonyl group is more preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is preferable. Is more preferable, and a methyl group (-CH ₃ ) or an ethyl group (-C ₂ H ₅ ) is particularly preferable.

As R ^2b and R ^4b , linear or branched alkyl groups having 1 to 10 carbon atoms which do not contain H or a carbonyl group are preferable, and H or 1 to 3 carbon atoms which do not have a substituent are preferable. The linear or branched alkyl group of is more preferable, H, a methyl group (-CH ₃ ) or an ethyl group (-C ₂ H ₅ ) is even more preferable, and H is particularly preferable.

In formula (b), R ^3b is an alkylene group having 1 to 10 carbon atoms which may have a substituent. When ^{a plurality of R 3b} exist, they may be the same or different.

The alkylene group preferably does not contain a carbonyl group.
In the alkylene group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkylene group preferably does not have any substituents.

As the alkylene group, 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 may be used. A linear or branched alkylene group having 1 to 10 carbon atoms containing no carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms containing no carbonyl group is preferable, and the number of carbon atoms having no substituent is preferable. more preferably a linear or branched alkylene group having 1 to 10, a methylene group _(-CH 2 -), ethylene group _{(-C 2 H} 4 -), isopropylene group (-CH _(CH 3) CH ₂ -) Or a propylene group (-C ₃ H _6- ) is more preferable.

Any two of R ^1b , R ^2b , R ^3b and R ^4b may be bonded to each other to form a ring, but it is preferable that the ring is not formed.

In equation (b), n is an integer of 1 or more. As n, an integer of 1 to 40 is preferable, an integer of 1 to 30 is more preferable, an integer of 5 to 25 is further preferable, and an integer of 5 to 9, 11 to 25 is particularly preferable.

In equation (b), p and q are independently integers greater than or equal to 0. As p, an integer of 0 to 10 is preferable, and 0 or 1 is more preferable. As q, an integer of 0 to 10 is preferable, and an integer of 0 to 5 is more preferable.

It is preferable that n, p and q are integers having a total of 5 or more. It is more preferable that the sum of n, p and q is an integer of 8 or more. The sum of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and even more preferably an integer of 40 or less.

In formula (b), X ^b is H, a metal atom, NR ^5b ₄ , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a substituent. It is a good phosphonium and R ^5b is an H or an organic group. The four ^R5b may be the same or different. As R ^5b , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable. X ^b may be a metal atom or NR ^5b ₄ (R ^5b is as described above).
As X ^b , H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR ^5b ₄ is preferable, and H, Na, K, Li or NH ₄ is more preferable because it is easily dissolved in water. further since the easily soluble in water, Na, K or NH ₄ are more preferred, particularly preferably Na or NH ₄ is, since removal is easy, NH ₄ being the most preferred. When X ^b is NH ₄ , the solubility of the above-mentioned surfactant in an aqueous medium is excellent, and the metal component is less likely to remain in PTFE or the final product.

In formula (b), L is a single bond, -CO ₂ -B- *, -OCO-B- *, -CONR ^6b -B- *, -NR ^{6b CO-B- *, or -CO- (} However, the _{carbonyl group contained in -CO 2} -B-, -OCO-B-, -CONR ^{6b -B-, and -NR 6} CO-B- is excluded), and B has a single bond or a substituent. It is an alkylene group having 1 to 10 carbon atoms which may be used, and R ^6b is an alkyl group having 1 to 4 carbon atoms which may have H or a substituent. The alkylene group preferably has 1 to 5 carbon atoms. Further, ^{it is more preferable that R 6} is an H or a methyl group. * Refers to the side in the equation _{that binds to -OSO 3} X ^b.

L is preferably a single bond.

（式中、Ｒ^１ｂ、Ｒ^２ｂ、Ｌ、ｎ及びＸ^ｂは、上記のとおり。）で示される化合物が好ましい。The surfactant (b) has the following formula:

(In the formula, R ^1b , R ^2b , L, n and X ^b are as described above.) The compound represented by the above is preferable.

For the surfactant (b), it is preferable that the integrated value of the total peak intensities observed in the region of chemical shift 2.0 to 5.0 ppm is 10% or more in ^{the 1 H-NMR spectrum.}

For the surfactant (b), it is preferable that the integrated value of the total peak intensities observed in the region of chemical shift 2.0 to 5.0 ppm is within the above range in ^{the 1 H-NMR spectrum.} In this case, the surfactant preferably has a ketone structure in the molecule.

In the surfactant (b), the integral value is more preferably 15 or more, more preferably 95 or less, more preferably 80 or less, still more preferably 70 or less.

The above integrated value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

The surfactant (c) will be described.

In the formula (c), R ^1c is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.
When the number of carbon atoms is 3 or more, the alkyl group may contain a carbonyl group (-C (= O)-) between two carbon atoms. Further, when the number of carbon atoms is 2 or more, the above-mentioned alkyl group may contain the above-mentioned carbonyl group at the end of the above-mentioned alkyl group. That is, _{an acyl group such as an acetyl group represented by CH 3-} C (= O)-is also included in the alkyl group.
Further, the alkyl group may contain a monovalent or divalent heterocycle when the number of carbon atoms is 3 or more, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. In R ^1c , a divalent heterocycle may be inserted between two carbon atoms, or the divalent heterocycle may be located at the end and bonded to −C (= O) −. A monovalent heterocycle may be located at the end of the alkyl group.

In the present specification, the "carbon number" of the alkyl group includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocyclic ring. For example, the group represented by CH _3- C (= O) -CH _2- has 3 carbon atoms, and CH _3- C (= O) -C ₂ H _4- C (= O) -C ₂ H ₄ The group represented by − has 7 carbon atoms, and the group represented by CH ₃ −C (= O) − has 2 carbon atoms.

In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond may be substituted. It is preferably not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^101c (in the formula, R ^101c is an alkyl group).
In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.

In formula (c), R ^2c and R ^3c are independently single-bonded or divalent linking groups.
It is preferable that R ^2c and R ^3c are independently single-bonded or linear or branched alkylene groups having 1 or more carbon atoms or cyclic alkylene groups having 3 or more carbon atoms.
The alkylene group constituting R ^2c and R ^3c preferably does not contain a carbonyl group.

In the alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond may be substituted. It is preferably not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^102c (in the formula, R ^102c is an alkyl group).
In the alkylene group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkylene group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.

R ^1c , R ^2c and R ^3c have a total of 5 or more carbon atoms. As the total number of carbon atoms, 7 or more is preferable, 9 or more is more preferable, 20 or less is more preferable, 18 or less is more preferable, and 15 or less is further preferable.
Any two of R ^1c , R ^2c and R ^3c may be bonded to each other to form a ring.

In the formula (c), in the formula, A ^c is -COOX ^c or -SO ₃ X ^c (X ^c is H, a metal atom, NR ^4c ₄ , an imidazolium which may have a substituent, a substituent. Is a pyridinium which may have a substituent or a phosphonium which may have a substituent, and ^R4c is H or an organic group, which may be the same or different). As R ^4c , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable.
As ^Xc , H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR ^4c ₄ is preferable, and H, Na, K, Li or NH ₄ is more preferable because it is easily dissolved in water. further since the easily soluble in water, Na, K or NH ₄ are more preferred, particularly preferably Na or NH ₄ is, since removal is easy, NH ₄ being the most preferred. When X ^c is NH ₄ , the solubility of the above-mentioned surfactant in an aqueous medium is excellent, and the metal component is less likely to remain in PTFE or the final product.

R ^1c includes a linear or branched alkyl group having 1 to 8 carbon atoms that does not contain a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms that does not contain a carbonyl group, and 1 to 10 carbonyl groups. A linear or branched alkyl group having 2 to 45 carbon atoms, a cyclic alkyl group having 3 to 45 carbon atoms including a carbonyl group, or a monovalent or divalent complex having 3 to 45 carbon atoms. A ring-containing alkyl group is preferred.

（式中、ｎ^１１ｃは０〜１０の整数であり、Ｒ^１１ｃは炭素数１〜５の直鎖状又は分岐鎖状のアルキル基又は炭素数３〜５の環状のアルキル基であり、Ｒ^１２ｃは炭素数０〜３のアルキレン基である。ｎ^１１ｃが２〜１０の整数である場合、Ｒ^１２ｃは各々同じであっても異なっていてもよい。）で示される基がより好ましい。Further, as R ^1c , the following formula:

(In the formula, n ^11c is an integer of 0 to 10, R ^11c is a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, and R ^12c. Is an alkylene group having 0 to 3 carbon atoms. When n ^11c is an integer of 2 to 10, R ^12c may be the same or different from each other.) Is more preferable.

As n ^11c , an integer of 0 to 5 is preferable, an integer of 0 to 3 is more preferable, and an integer of 1 to 3 is further preferable.

The alkyl group as R ^11c preferably does not contain a carbonyl group.
In ^{the above alkyl group as R 11c} , the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond. It may be, but it is preferable that it is not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^103c (in the formula, R ^103c is an alkyl group).
In ^{the above alkyl group as R 11c} , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be halogen. Although it may be substituted with an atom, it is preferably a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom.

R ^12c is an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3.
The alkylene group as R ^12c may be linear or branched.
The alkylene group as R ^12c preferably does not contain a carbonyl group. The R ^12c, an ethylene group _(-C 2 _{H 4} -) or propylene group _(-C 3 _{H 6} -) is more preferred.
In the ^{alkylene group as R 12c} , the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxy group (-OH) or a monovalent organic group containing an ester bond. It may be, but it is preferable that it is not substituted with any functional group.
Examples of the monovalent organic group containing the ester bond include a group represented by the formula: -OC (= O) -R ^104c (in the formula, R ^104c is an alkyl group).
In ^{the above alkylene group as R 12c} , 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be halogen. Although it may be substituted with an atom, it is preferably a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or a chlorine atom.

As R ^2c and R ^3c , independently, an alkylene group having 1 or more carbon atoms which does not contain a carbonyl group is preferable, an alkylene group having 1 to 3 carbon atoms which does not contain a carbonyl group is more preferable, and an ethylene group (-C ₂ H) is preferable. ₄ -) or propylene group _(-C 3 _{H 6} -) is more preferred.

The surfactant (d) will be described.

In the formula (d), R ^1d is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent or a cyclic alkyl having 3 or more carbon atoms which may have a substituent. It is a group.
When the number of carbon atoms is 3 or more, the alkyl group may contain a monovalent or divalent heterocycle, or may form a ring. As the heterocycle, an unsaturated heterocycle is preferable, an oxygen-containing unsaturated heterocycle is more preferable, and examples thereof include a furan ring. In R ^1d , a divalent heterocycle may be inserted between two carbon atoms, or the divalent heterocycle may be located at the end and bonded to −C (= O) −. A monovalent heterocycle may be located at the end of the alkyl group.

In the present specification, the "carbon number" of the alkyl group includes the number of carbon atoms constituting the heterocycle.

Examples of the substituent that the above alkyl group as R ^1d may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. A hydroxy group is preferable, and a methyl group and an ethyl group are particularly preferable.

The alkyl group as R ^1d preferably does not contain a carbonyl group.
In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkyl group preferably does not have any substituents.

As R ^1d , 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 preferable. , A linear or branched alkyl group having 1 to 10 carbon atoms containing no carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms containing no carbonyl group is more preferable, and the number of carbon atoms having no substituent is preferable. A linear or branched alkyl group of 1 to 10 is even more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is even more preferable, and a methyl group (-CH). ₃ ) or an ethyl group (-C ₂ H ₅ ) is particularly preferable, and a methyl group (-CH ₃ ) is most preferable.

In formula (d), R ^2d and R ^4d are independently H or substituents. The plurality of R ^2d and R ^4d may be the same or different from each other.

As the substituent as R ^2d and R ^4d , 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, and a hydroxy group are preferable. Groups and ethyl groups are particularly preferred.

The alkyl groups as R ^2d and R ^4d preferably do not contain a carbonyl group. In the above alkyl group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkyl group preferably does not have any substituents.

The above-mentioned alkyl groups as R ^2d and R ^4d include 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 preferable, a linear or branched alkyl group having 1 to 10 carbon atoms containing no carbonyl group is more preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is preferable. Is more preferable, and a methyl group (-CH ₃ ) or an ethyl group (-C ₂ H ₅ ) is particularly preferable.

As R ^2d and R ^4d , linear or branched alkyl groups having 1 to 10 carbon atoms which do not contain H or a carbonyl group are preferable, and H or 1 to 3 carbon atoms which do not have a substituent are preferable. The linear or branched alkyl group of is more preferable, H, a methyl group (-CH ₃ ) or an ethyl group (-C ₂ H ₅ ) is even more preferable, and H is particularly preferable.

In formula (d), R ^3d is an alkylene group having 1 to 10 carbon atoms which may have a substituent. When ^{a plurality of R3d} are present, they may be the same or different.

The alkylene group preferably does not contain a carbonyl group.
In the alkylene group, 75% or less of the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom. However, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
The alkylene group preferably does not have any substituents.

As the alkylene group, 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 may be used. A linear or branched alkylene group having 1 to 10 carbon atoms containing no carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms containing no carbonyl group is preferable, and the number of carbon atoms having no substituent is preferable. more preferably a linear or branched alkylene group having 1 to 10, a methylene group _(-CH 2 -), ethylene group _{(-C 2 H} 4 -), isopropylene group (-CH _(CH 3) CH ₂ -) Or a propylene group (-C ₃ H _6- ) is more preferable.

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

In equation (d), n is an integer of 1 or more. As n, an integer of 1 to 40 is preferable, an integer of 1 to 30 is more preferable, and an integer of 5 to 25 is further preferable.

In equation (d), p and q are independently integers greater than or equal to 0. As p, an integer of 0 to 10 is preferable, and 0 or 1 is more preferable. As q, an integer of 0 to 10 is preferable, and an integer of 0 to 5 is more preferable.

It is preferable that n, p and q are integers having a total of 6 or more. It is more preferable that the sum of n, p and q is an integer of 8 or more. The sum of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and even more preferably an integer of 40 or less.

Wherein (d), ^{A d} is _-SO 3 ^{X d} or -COOX ^{d (X d} has H, a metal atom, ^{NR 5d} _4, good imidazolium be substituted, the substituent It is a pyridinium which may be present or a phosphonium which may have a substituent, and ^R5d is an H or an organic group, which may be the same or different). As R ^5d , H or an organic group having 1 to 10 carbon atoms is preferable, and H or an organic group having 1 to 4 carbon atoms is more preferable. Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable. X ^d may be a metal atom or NR ^5d ₄ (R ^5d is as described above).
As X ^d , H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR ^5d ₄ is preferable, and H, Na, K, Li or NH ₄ is more preferable because it is easily dissolved in water. further since the easily soluble in water, Na, K or NH ₄ are more preferred, particularly preferably Na or NH ₄ is, since removal is easy, NH ₄ being the most preferred. When X ^d is NH ₄ , the solubility of the above-mentioned surfactant in an aqueous medium is excellent, and metal components are less likely to remain in PTFE or the final product.

In formula (d), L is a single bond, -CO ₂ ^{-B- *, -OCO} -B- *, -CONR ^6d -B- *, -NR 6d CO-B- *, or -CO- ( However, the _{carbonyl group contained in -CO 2} ^{-B-, -OCO} -B-, -CONR ^6d -B-, and -NR 6d CO-B- is excluded), and B has a single bond or a substituent. It is an alkylene group having 1 to 10 carbon atoms which may be used, and R ^6d is an alkyl group having 1 to 4 carbon atoms which may have H or a substituent. The alkylene group preferably has 1 to 5 carbon atoms. Further, ^{it is more preferable that the R 6d} is an H or a methyl group. * Refers to the side connected to ^{Ad in the equation.}

L is preferably a single bond.

The above-mentioned surfactant preferably has an integral value of the total peak intensity observed in the region of chemical shift 2.0 to 5.0 ppm of 10 or more in ^{the 1 H-NMR spectrum.}

For the above-mentioned surfactant, it is preferable that the integral value of the total peak intensities observed in the region of chemical shift 2.0 to 5.0 ppm ^{in the 1 H-NMR spectrum is within the above range.} In this case, the surfactant preferably has a ketone structure in the molecule.

In the surfactant, the integral value is more preferably 15 or more, more preferably 95 or less, more preferably 80 or less, still more preferably 70 or less.

The above integrated value is measured at room temperature in a heavy water solvent. Heavy water is 4.79 ppm.

A hydrocarbon-based surfactant obtained by radically treating or oxidizing the above-mentioned hydrocarbon-based surfactant can also be used.
The radical treatment may be any treatment as long as it generates radicals in the above-mentioned hydrocarbon-based surfactant. For example, deionized water and a hydrocarbon-based surfactant are added to the reactor, the reactor is sealed, and the system is sealed. This is a process in which the inside is replaced with nitrogen, the temperature of the reactor is raised and the pressure is increased, a polymerization initiator is charged, the reactor is stirred for a certain period of time, the reactor is depressurized until it reaches atmospheric pressure, and the reactor is cooled. The above-mentioned oxidation treatment is a treatment for adding an oxidizing agent to a hydrocarbon-based surfactant. Examples of the oxidizing agent include oxygen, ozone, hydrogen peroxide solution, manganese oxide (IV), potassium permanganate, potassium dichromate, nitric acid, sulfur dioxide and the like. In order to promote the radical treatment or the oxidation treatment, the radical treatment or the oxidation treatment may be carried out in a pH-adjusted aqueous solution. The pH of the aqueous solution for performing the radical treatment or the oxidation treatment is preferably less than 7, and the pH of the aqueous solution can be adjusted by using, for example, sulfuric acid, nitric acid, hydrochloric acid or the like.

In the step (II), for example, the polymerization reactor is charged with an aqueous dispersion containing the particles, TFE, an aqueous medium if necessary, a monomer other than TFE, a surfactant, and other additives, and the reactor is charged. It can be carried out by stirring the contents, keeping the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of a polymerization initiator to initiate the polymerization reaction. After the start of the polymerization reaction, a monomer, a polymerization initiator, a chain transfer agent, the above-mentioned surfactant and the like may be additionally added depending on the purpose. The above-mentioned surfactant may be added after the polymerization reaction has started.
The polymerization initiator is not particularly limited as long as it can generate radicals in the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Further, the polymerization can be started as a redox in combination with a reducing agent or the like. The concentration of the polymerization initiator is appropriately determined depending on the type of the monomer, the molecular weight of the target TFE polymer, and the reaction rate.
As the polymerization initiator, it is preferable to use an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator. The step (II) is preferably a step performed in the presence of an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator. In particular, it is preferable to use the above-mentioned oil-soluble peroxide or water-soluble peroxide as the polymerization initiator.

It is preferable that the step (II) is for polymerizing TFE in the absence of a fluorine-containing surfactant. "Substantially in the absence of a fluorine-containing surfactant" means that the amount of the fluorine-containing surfactant is 10% by mass or less with respect to the TFE polymer obtained by polymerization, preferably 1% by mass ppm. It is less than or equal to, more preferably 100 mass ppb or less, further preferably 10 mass ppb or less, and even more preferably 1 mass ppb or less.

The step (I) or step (II) may be further polymerized in the presence of a nucleating agent. The nucleating agent may be used only in the step (I), may be used only in the step (II), or may be used in both the step (I) and the step (II).

The nucleating agent is preferably at least one selected from the group consisting of, for example, fluoropolyethers, nonionic surfactants, and chain transfer agents.

The fluoropolyether itself provides a polymerization field and can be a nucleation site.

As the fluoropolyether, perfluoropolyether is preferable.

The fluoropolyether preferably has a repeating unit represented by the formulas (1a) to (1d).
(-CFCF _{3- CF 2-} O-) _n (1a)
(-CF _2- CF _2- CF _2- O-) _n (1b)
_{(-CF 2 -CF 2 -O-) n} - (- CF 2 -O-) m (1c)
_{(-CF 2 -CFCF 3 -O-) n} - (- CF 2 -O-) m (1d)
(In equations (1a) to (1d), m and n are integers of 1 or more.)

The fluoropolyether is preferably a fluoropolyether acid or a salt thereof, and the fluoropolyether acid is preferably a carboxylic acid, a sulfonic acid, a sulfonic acid, or a phosphonic acid, and more preferably a carboxylic acid. preferable. Among the fluoropolyether acid or a salt thereof, a salt of fluoropolyether acid is preferable, an ammonium salt of fluoropolyether acid is more preferable, and an ammonium salt of fluoropolyethercarboxylic acid is further preferable.

The fluoropolyether acid or a salt thereof can have any chain structure in which the oxygen atom in the main chain of the molecule is separated by a saturated fluorocarbon group having 1 to 3 carbon atoms. Two or more types of fluorocarbon groups can be present in the molecule.

The above fluoropolyether acid or a salt thereof has the following formula:
_{CF 3 -CF 2 -CF 2 -O (} -CFCF 3 -CF 2 -O-) n CFCF 3 -COOH, CF 3 -CF 2 -CF 2 -O (-CF 2 -CF 2 -CF 2 -O- ) _N- CF _2- CF ₂ COOH, or
_{HOOC-CF 2 -O (-CF 2} -CF 2 -O-) n - (- CF 2 -O-) m CF 2 COOH ( wherein, m and n are as defined above.)
It is preferably a compound represented by or a salt thereof.

These structures are described in J. Mol. Apple. Polymer Sci. , 57, 797 (1995), examined by Kasai. As disclosed herein, such fluoropolyethers can have a carboxylic acid group or a salt thereof at one end or both ends. Similarly, such fluoropolyethers may have a sulfonic acid or phosphonic acid group or a salt thereof at one end or both ends. In addition, fluoropolyethers having acid functional groups at both ends may have different groups at each end. For monofunctional fluoropolyethers, the other end of the molecule is usually hyperfluorinated, but may contain hydrogen or chlorine atoms.

A fluoropolyether having an acid group at one end or both ends has at least two ether oxygens, preferably at least four ether oxygens, and even more preferably at least six ether oxygens. Preferably, at least one of the fluorocarbon groups that separates the ether oxygen, more preferably at least two of such fluorocarbon groups, has two or three carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups that separate ether oxygen have 2 or 3 carbon atoms. Also, preferably, the fluoropolyether has at least 15 carbon atoms in total, and for example, the preferable minimum value of n or n + m in the above repeating unit structure is at least 5. Two or more fluoropolyethers having an acid group at one end or both ends can be used in the methods according to the present disclosure. Typically, unless special care is taken in the production of a particular fluoropolyether compound of a single species, the fluoropolyether may contain multiple compounds in various proportions within the molecular weight range relative to the average molecular weight. ..

The fluoropolyether preferably has a number average molecular weight of 800 g / mol or more. Since it may be difficult to disperse the fluoropolyether in an aqueous medium, the number average molecular weight is preferably less than 6000 g / mol. The fluoropolyether preferably has a number average molecular weight of 800 to 3500 g / mol, and more preferably 1000 to 2500 g / mol.

The amount of the fluoropolyether is preferably 5 to 3000 mass ppm, more preferably 5 to 2000 mass ppm, a further preferable lower limit is 10 mass ppm, and a further preferable upper limit is 100. The mass is ppm.

The nonionic surfactant itself provides a polymerization field and can become a nucleation site by providing a large number of low molecular weight fluoropolymers by chain transfer of radicals in the early stage.

Examples of the nonionic surfactant as the nucleating agent include the above-mentioned nonionic surfactant, and a fluorine-free nonionic surfactant is preferable. For example, ether-type nonionic surfactants such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene alkylene alkyl ethers; polyoxyethylene derivatives such as ethylene oxide / propylene oxide block copolymers; sorbitan fatty acids. Estel-type nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters; amine-based non-amines such as polyoxyethylene alkylamines and alkylalkanolamides. Ionic surfactants; and the like.

In the above nonionic surfactant, the hydrophobic group may be any of an alkylphenol group, a linear alkyl group and a branched alkyl group.

Examples of the nonionic surfactant include the following general formula (i).
R ^3- O-A ^1- H (i)
(In the formula, R ³ is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A ¹ is a polyoxyalkylene chain.) Can be mentioned. The number of carbon atoms of R ³ is preferably 10 to 16, 12 to 16 is more preferable. The number of carbon atoms of R ³ is 18 easy good dispersion stability of the aqueous dispersion obtained is not more than. Also difficult to handle for the flow temperature is higher number of carbon atoms in R ³ exceeds 18. When ^{the carbon number of R 3} is smaller than 8, the surface tension of the aqueous dispersion becomes high, and the permeability and wettability tend to decrease.

The polyoxyalkylene chain may be composed of oxyethylene and oxypropylene. It is a polyoxyalkylene chain consisting of an average number of repetitions of an oxyethylene group of 5 to 20 and an average number of repetitions of an oxypropylene group of 0 to 2, and is a hydrophilic group. The number of oxyethylene units can include either the broad or narrow monomodal distribution normally provided, or the broader or bimodal distribution obtained by blending. When the average number of repetitions of the oxypropylene group is more than 0, the oxyethylene group and the oxypropylene group in the polyoxyalkylene chain may be arranged in a block shape or a random shape.
From the viewpoint of the viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain composed of an average number of repetitions of 7 to 12 for oxyethylene groups and an average number of repetitions of 0 to 2 for oxypropylene groups is preferable. In particular, ^{it is preferable that A 1} has an average of 0.5 to 1.5 oxypropylene groups because low foaming property is good.

More preferably, R ³ is (R') (R'') HC-, where R'and R'' are the same or different straight chain, branched chain, or cyclic alkyl groups. The total amount of carbon atoms is at least 5, preferably 7 to 17. Preferably, at least one of R'or R'' is a branched or cyclic hydrocarbon group.

Specific examples of the nonionic surfactant include C ₁₃ H _27- O- (C ₂ H ₄ O) _10- H, C ₁₂ H _25- O- (C ₂ H ₄ O) _10- H, C. _{10 H 21 CH (CH 3)} CH 2 -O- (C 2 H 4 O) 9 -H, C 13 H 27 -O- (C 2 H 4 O) 9 - (CH (CH 3) CH 2 O) -H, C ₁₆ H _33- O- (C ₂ H ₄ O) _10- H, HC (C ₅ H ₁₁ ) (C ₇ H ₁₅ ) -O- (C ₂ H ₄ O) _9- H, etc. Be done. Examples of commercially available nonionic surfactants include Genapol X080 (product name, manufactured by Clariant), Neugen TDS-80 (trade name), and the Neugen TDS series (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Leocol TD-90 (trade name) as an example Leocol TD series (manufactured by Lion), Lionol (registered trademark) TD series (manufactured by Lion), T-Det A138 (trade name) as an example T-Det A Examples thereof include a series (manufactured by Harcros Chemicals) and a Targitol (registered trademark) 15S series (manufactured by Dow Chemicals).

The nonionic surfactant has an ethoxylate of 2,6,8-trimethyl-4-nonanol having an average of about 4 to about 18 ethylene oxide units, an average of about 6 to about 12 ethylene oxide units 2, It is also preferable that it is an ethoxylate of 6,8-trimethyl-4-nonanol or a mixture thereof. This type of nonionic surfactant is also commercially available, for example, as TERGITOR TMN-6, TERGITOR TMN-10, and TERGITOR TMN-100X (all product names, manufactured by Dow Chemical).

Further, the hydrophobic group of the nonionic surfactant may be any of an alkylphenol group, a linear alkyl group and a branched alkyl group.
For example, as a nonionic surfactant, the following general formula (ii)
R ^4- C ₆ H _4- O-A ^2- H (ii)
(In the formula, R ⁴ is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms, and A ² is a polyoxyalkylene chain.). Examples thereof include ethylene alkylphenyl ether-based nonionic compounds. Specific examples of the polyoxyethylene alkyl phenyl ether-based nonionic compound include Triton X-100 (trade name, manufactured by Dow Chemical Co., Ltd.) and the like.

Examples of the nonionic surfactant include polyol compounds. Specific examples thereof include those described in International Publication No. 2011/014715.
A typical example of a polyol compound is a compound having one or more sugar units as a polyol unit. The sugar unit may be modified to contain at least one long chain. Suitable polyol compounds containing at least one long chain moiety include, for example, alkyl glycosides, modified alkyl glycosides, sugar esters, and combinations thereof. Examples of sugars include, but are not limited to, monosaccharides, oligosaccharides, and sorbitan. Examples of monosaccharides include pentasaccharides and hexasaccharides. Typical examples of monosaccharides include ribose, glucose, galactose, mannose, fructose, arabinose and xylose. Examples of oligosaccharides include 2 to 10 identical or different monosaccharide oligomers. Examples of oligosaccharides include, but are not limited to, saccharose, maltose, lactose, raffinose, and isomaltose.

Typically, a suitable sugar for use as a polyol compound is a five-membered ring of four carbon atoms and one heteroatom (typically oxygen or sulfur, but preferably an oxygen atom). Examples thereof include a cyclic compound containing, or a cyclic compound containing a six-membered ring of five carbon atoms and one heteroatom as described above, preferably an oxygen atom. They further contain at least 2 or at least 3 hydroxy groups (−OH groups) attached to the carbocyclic atom. Typically, the sugar is a hydrogen atom of a hydroxy group (and / or a hydroxyalkyl group) attached to a carbocyclic atom such that an ether or ester bond is formed between the long chain residue and the sugar moiety. One or more of them are denatured in that they are replaced by long chain residues.
The sugar-based polyol may contain one sugar unit or a plurality of sugar units. One sugar unit or a plurality of sugar units may be modified with the long chain portion as described above. Specific examples of sugar-based polyol compounds include glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof.

（式中、ｘは、０、１、２、３、４、又は５を表し、Ｒ^１及びＲ^２は、独立して、Ｈ又は少なくとも６個の炭素原子を含有する長鎖単位を表すが、但しＲ^１及びＲ^２のうちの少なくとも１個はＨではない）によって表される化合物が挙げられる。Ｒ^１及びＲ^２の典型例としては、脂肪族アルコール残基が挙げられる。脂肪族アルコールの例としては、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール（ラウリルアルコール）、テトラデカノール、ヘキサデカノール（セチルアルコール）、ヘプタデカノール、オクタデカノール（ステアリルアルコール）、エイコサン酸、及びこれらの組み合わせ挙げられる。
上記の式は、ピラノース形態のグルコースを示すアルキルポリグルコシドの特定の例を表すが、他の糖又は同じ糖であるが異なる鏡像異性体又はジアステレオマー形態である糖を用いてもよいことが理解される。
アルキルグルコシドは、例えば、グルコース、デンプン、又はｎ−ブチルグルコシドと脂肪族アルコールとの酸触媒反応によって入手可能であり、これからは、典型例に、様々なアルキルグルコシドの混合物が得られる（Ａｌｋｙｌｐｏｌｙｇｙｌｃｏｓｉｄｅ，Ｒｏｍｐｐ，Ｌｅｘｉｋｏｎ Ｃｈｅｍｉｅ，Ｖｅｒｓｉｏｎ ２．０，Ｓｔｕｔｔｇａｒｔ／Ｎｅｗ Ｙｏｒｋ，Ｇｅｏｒｇ Ｔｈｉｅｍｅ Ｖｅｒｌａｇ，１９９９）。脂肪族アルコールの例としては、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール（ラウリルアルコール）、テトラデカノール、ヘキサデカノール（セチルアルコール）、ヘプタデカノール、オクタデカノール（ステアリルアルコール）、エイコサン酸、及びこれらの組み合わせ挙げられる。また、アルキルグルコシドは、Ｃｏｇｎｉｓ ＧｍｂＨ，Ｄｕｓｓｅｌｄｏｒｆ，Ｇｅｒｍａｎｙから商品名ＧＬＵＣＯＰＯＮ又はＤＩＳＰＯＮＩＬとして市販されている。Preferred types of polyol compounds are alkyl or modified alkyl glucosides. These types of surfactants contain at least one glucose moiety.

(In the formula, x represents 0, 1, 2, 3, 4, or 5, and R ¹ and R ² independently represent H or a long chain unit containing at least 6 carbon atoms. However, at least one of ^{R 1} and R ^{2 is not H).} Typical examples of R ¹ and R ² include aliphatic alcohol residues. Examples of fatty alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), Eikosanoic acid and combinations thereof can be mentioned.
The above formula represents a specific example of an alkylpolyglucoside exhibiting a pyranose form of glucose, although other sugars or sugars of the same but different enantiomers or diastereomeric forms may be used. Understood.
Alkyl glucosides are available, for example, by acid-catalyzed reactions of glucose, starch, or n-butyl glucosides with fatty alcohols, from which a mixture of various alkyl glucosides is typically obtained (Alkylplygylcosine, Ronmp. , Lexikon Chemie, Version 2.0, Stuttgart / New York, Georg Timeme Verlag, 1999). Examples of fatty alcohols include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), Eikosanoic acid and combinations thereof can be mentioned. Alkyl glucoside is commercially available from Cognis GmbH, Dusseldorf, Germany under the trade name GLUCOPON or DISPONIL.

Other nonionic surfactants include bifunctional block copolymers supplied by BASF as the Pluronic® R series and tridecyl alcohol alkoxylates supplied by BASF as the Iconol® TDA series. Can be mentioned.

The nonionic surfactant is at least selected from the group consisting of the nonionic surfactant represented by the general formula (i) and the nonionic surfactant represented by the general formula (ii). One is preferable, and the nonionic surfactant represented by the general formula (i) is more preferable.

The nonionic surfactant preferably does not contain an aromatic moiety.

The amount of the nonionic surfactant is preferably 0.1 to 0.000000001% by mass, more preferably 0.01 to 0.000001% by mass, based on the aqueous medium.

The chain transfer agent can become a nucleation site by giving a large number of low molecular weight fluoropolymers by chain transfer of radicals in the initial stage.

Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate and dimethyl succinate, as well as isopentane, methane, ethane, propane, isobutane, methanol, ethanol and isopropanol. , Acetone, various mercaptans, various halogenated hydrocarbons such as carbon tetrachloride, cyclohexane and the like.

A bromine compound or an iodine compound may be used as the chain transfer agent. Examples of the polymerization method using a bromine compound or an iodine compound include a method of polymerizing a fluoromonomer in an aqueous medium in the presence of a bromine compound or an iodine compound in a substantially anoxic state (for example). Iodine transfer polymerization method). Typical examples of the bromine compound or iodine compound used include, for example, the general formula:
R ^a I _x Br _y
(In the formula, x and y are integers of 0 to 2, respectively, and satisfy 1 ≦ x + y ≦ 2, and ^Ra is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro. Examples thereof include a compound represented by a hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms and may contain an oxygen atom). By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer and functions as a cross-linking point.

Examples of the bromine compound or iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, and 1 , 5-Diode-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodine perfluoro hexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF ₂ CF ₂ Br, BrCF _{2 CFBrOCF 3} , 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3- Iodine perfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo and diiodomonobromo substituents of benzene, and (2). -Iodine ethyl) and (2-bromoethyl) substituents can be mentioned, and these compounds may be used alone or in combination with each other.

Among these, at least one selected from the group consisting of alkanes and alcohols is preferable from the viewpoints of polymerization reactivity, cross-linking reactivity, availability and the like. The carbon number of the alkane is preferably 1 to 6, more preferably 1 to 5. The alcohol has preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms. As the chain transfer agent, at least one selected from the group consisting of methane, ethane, propane, isobutane, methanol, ethanol, and isopropanol is particularly preferable.

The amount of the chain transfer agent is preferably 0.001 to 10000 mass ppm with respect to the aqueous medium. The amount of the chain transfer agent is more preferably 0.01 mass ppm or more, further preferably 0.05 mass ppm or more, and particularly preferably 0.1 mass ppm or more with respect to the aqueous medium. Further, 1000 mass ppm or less is more preferable, 500 mass ppm or less is further preferable, and 100 mass ppm or less is particularly preferable with respect to the aqueous medium.

In the above polymerization step, the nucleating agent is put into the aqueous medium before the polymerization reaction is started or before the polymerization reaction proceeds and the concentration of the TFE polymer in the aqueous dispersion reaches 5.0% by mass. It is preferable to add to. By adding a nucleating agent at the initial stage of polymerization, more particles can be generated during polymerization, and further, primary particles having a smaller average primary particle size and aspect ratio can be obtained. That is, the nucleating agent may be added before the start of the polymerization, at the same time as the start of the polymerization, or after the start of the polymerization, during the period when the nuclei of the TFE polymer particles are formed. May be good.

The time to add the nucleating agent is before the start of polymerization or before the polymerization reaction proceeds and the concentration of the TFE polymer in the aqueous dispersion reaches 5.0% by mass, preferably before the start of polymerization or TFE. Before the concentration of the polymer reaches 3.0% by mass, more preferably before the start of polymerization or before the concentration of the TFE polymer reaches 1.0% by mass, still more preferably before the start of polymerization or the TFE polymer. Before the concentration of 5 reaches 0.5% by mass, and particularly preferably before the start of the polymerization or at the same time as the start of the polymerization.

The amount of the nucleating agent to be added can generate more particles during polymerization, and further, primary particles having a smaller average primary particle size can be obtained. Therefore, with respect to the obtained TFE polymer, It is preferably 0.001 to 5000 mass ppm. The lower limit of the amount of the nucleating agent is 0.01 mass ppm, 0.05 mass ppm, and 0.1 mass ppm in the preferred order. The upper limit of the amount of the nucleating agent is 2000 mass ppm, 1000 mass ppm, 500 mass ppm, 100 mass ppm, 50 mass ppm, and 10 mass ppm in the preferred order.

Further, in the above steps (I) and (II), additives can be used to stabilize each compound. Examples of the additive include a buffer, a pH adjuster, a stabilizing aid, a dispersion stabilizer and the like.

As the stabilizing aid, paraffin wax, fluorinated oil, fluorinated solvent, silicone oil and the like are preferable. The stabilizing aid may be used alone or in combination of two or more. Paraffin wax is more preferable as the stabilizing aid. The paraffin wax may be liquid, semi-solid, or solid at room temperature, but saturated hydrocarbons having 12 or more carbon atoms are preferable. The melting point of the paraffin wax is usually preferably 40 to 65 ° C, more preferably 50 to 65 ° C.

The amount of the stabilizing aid used is preferably 0.1 to 12% by mass, more preferably 0.1 to 8% by mass, based on the mass of the aqueous medium used. It is desirable that the stabilizing aid is sufficiently hydrophobic and is completely separated from the TFE polymer dispersion after the polymerization of the TFE polymer and does not become a contaminant component.

The TFE polymer obtained by the production method of the present disclosure contains 40 mol% or more of the polymerization units based on TFE with respect to all the polymerization units of the TFE polymer. The content of the polymerization unit based on TFE is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more. ..
The TFE polymer contains 60 mol% or less of polymerization units based on a monomer other than TFE with respect to all the polymerization units of the TFE polymer. The polymerization unit based on TFE is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, still more preferably 20 mol% or less, and particularly preferably 10 mol% or less.

In the present specification, the content of each monomer unit constituting the TFE polymer is appropriately combined with NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and other known methods depending on the type of monomer. Can be calculated by
Further, the content of each monomer unit constituting the TFE polymer can also be obtained by calculation from the addition amount of the monomer used for the polymerization.

Hereinafter, the TFE polymer obtained by the production method of the present disclosure will be described in more detail.

The TFE polymer may be a TFE homopolymer or a copolymer of TFE and a monomer other than TFE.
The TFE polymer may also be a fluororesin or a fluororubber, but a fluororesin is preferable.

For example, a copolymer consisting of (1) TFE, (2) one or more fluorine-containing monomers other than TFE having 2 to 8 carbon atoms, particularly VDF, HFP or CTFE, and (3) other monomers. It may be a polymer. Examples of the above-mentioned (3) other monomer include fluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms; fluorodioxol; perfluoroalkylethylene; ω-. Hydroperfluoroolefin; perfluoroallyl ether and the like can be mentioned.

The TFE polymer may also be a copolymer of (1) TFE and (2) one or more fluorine-free monomers. Examples of the fluorine-free monomer include alkenes such as ethylene and propylene; vinyl esters; and vinyl ethers. The TFE polymer is also a copolymer of TFE, one or more fluorine-containing monomers having 2 to 8 carbon atoms, and one or more fluorine-free monomers. May be good.

The TFE polymer includes (1) TFE and (2) a copolymer containing a polymerization unit based on VDF; (1) TFE, (2) VDF, and (3) 2 to 8 carbon atoms. Copolymers containing TFE and (4) fluoroolefins other than VDF (particularly HFP or CTFE) based; (1) TFE, (2) VDF, (3) TFE having 2 to 8 carbon atoms and Includes fluoroolefins other than VDF (particularly HFP or CTFE) and (4) perfluoro (alkyl vinyl ether) -based polymerization units having an alkyl group having 1 to 5 carbon atoms (particularly 1 to 3 carbon atoms). It may be a copolymer or the like.

Examples of the TFE polymer include (1) TFE, (2) CTFE, (3) one or more TFE having 2 to 8 carbon atoms and fluoroolefins other than CTFE, particularly HFP, and (4). ) A copolymer composed of perfluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms may be used.
The TFE polymer may also be a copolymer of (1) TFE, (2) CTFE, and (3) one or more fluorine-free monomers, and may be a fluoropolymer. Examples thereof include alkenes such as ethylene and propylene; vinyl esters; vinyl ethers and the like.

The TFE polymer produced by the production method of the present disclosure can be glassy, plastic or elastomeric. These are amorphous or partially crystalline and can be subjected to compression firing, melting or non-melting.

In the production method of the present disclosure, for example, (I) a tetrafluoroethylene polymer [TFE polymer (PTFE)] as a non-melt processable fluororesin, and (II) an ethylene / TFE co-weight as a melt processable fluororesin. Combined [ETFE], TFE / HFP copolymer [FEP], TFE / perfluoro (alkyl vinyl ether) copolymer [PFA, MFA, etc.], TFE / perfluoroallyl ether copolymer, TFE / VDF copolymer, The electrolyte polymer precursor is (III) as a fluororubber, a TFE / propylene copolymer, a TFE / propylene / third monomer copolymer (the third monomer is VDF, HFP, CTFE, fluoroalkyl vinyl ethers, etc.), and the like. A copolymer composed of TFE and fluoroalkyl vinyl ethers; and a thermoplastic elastomer such as a VDF / TFE / HFP copolymer can be preferably produced.

As the TFE polymer, a TFE polymer having a fluorine substitution rate of 50% or more calculated by the following formula is more preferable, a TFE polymer having a fluorine substitution rate of more than 50% is further preferable, and the fluorine substitution rate is 55. % Or more TFE polymer is even more preferable, TFE polymer having a fluorine substitution rate of 60% or more is even more preferable, TFE polymer having a fluorine substitution rate of 75% or more is even more preferable, and the fluorine substitution rate is even more preferable. A TFE polymer of 80% or more is particularly preferable, and a TFE polymer having a fluorine substitution rate of 90 to 100%, that is, a perfluoropolymer is most preferable.
(formula)
Fluorine substitution rate (%) = (number of fluorine atoms bonded to carbon atoms constituting the TFE polymer) / ((number of hydrogen atoms bonded to carbon atoms constituting the TFE polymer) + (constituting the TFE polymer) Number of fluorine atoms and chlorine atoms bonded to carbon atoms)) x 100

As the perfluoropolymer, the TFE polymer having a fluorine substitution rate of 95 to 100% is more preferable, PTFE, FEP, or PFA is more preferable, and PTFE is particularly preferable.

The above-mentioned (I) non-melt processable fluororesin, (II) melt processable fluororesin and (III) fluororubber preferably produced by the production method of the present disclosure are preferably produced in the following embodiments.

(I) Non-melt processable fluororesin (polytetrafluoroethylene)
In the production method of the present disclosure, the polymerization of TFE is usually carried out at a polymerization temperature of 10 to 150 ° C. and a polymerization pressure of 0.05 to 5 MPaG. For example, the polymerization temperature is more preferably 30 ° C. or higher, further preferably 50 ° C. or higher. Further, 120 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable. The polymerization pressure is more preferably 0.3 MPaG or more, further preferably 0.5 MPaG or more, still more preferably 5.0 MPaG or less, still more preferably 3.0 MPaG or less. In particular, from the viewpoint of improving the yield of the fluoropolymer, 1.0 MPaG or more is preferable, 1.2 MPaG or more is more preferable, 1.5 MPaG or more is further preferable, and 2.0 MPaG or more is more preferable.

In one embodiment, in the above-mentioned polymerization, pure water is charged in a pressure-resistant reaction vessel equipped with a stirrer, deoxidized, TFE is charged, the temperature is set to a predetermined temperature, a polymerization initiator is added, and the reaction is started. If the pressure decreases as the reaction progresses, additional TFE is continuously or intermittently supplied to maintain the initial pressure. When a predetermined amount of TFE is supplied, the supply is stopped, the TFE in the reaction vessel is purged, the temperature is returned to room temperature, and the reaction is terminated. Additional TFE may be supplied continuously or intermittently so that the pressure does not drop.

When the TFE polymer is polytetrafluoroethylene (PTFE), various conventionally known modified monomers can be used in combination with TFE. In the present specification, the above-mentioned PTFE includes not only a TFE homopolymer but also a copolymer of TFE and a modified monomer which is non-meltable (hereinafter referred to as "modified PTFE"). It is a concept.

The content of the polymerization unit based on the modified monomer of the modified PTFE (hereinafter, also referred to as “modified monomer unit”) may be in the range of 0.00001 to 1.0% by mass with respect to the total polymerization units of PTFE. preferable. As the lower limit of the content of the modified monomer unit, 0.0001% by mass is more preferable, 0.001% by mass is further preferable, and 0.005% by mass is further more preferable. The upper limit of the content of the modified monomer unit is 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10. It is mass% and 0.05 mass%. In the present disclosure, the modified monomer unit means a part of the molecular structure of PTFE that is derived from the modified monomer.

In the present disclosure, the content of each monomer unit constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. Further, the content of each monomer unit constituting PTFE can also be obtained by calculation from the addition amount of the modified monomer used for the polymerization.

The modified monomer is not particularly limited as long as it can be copolymerized with TFE, and examples thereof include fluoromonomers and non-fluoromonomers.

The non-fluoromonomer is not particularly limited, and the general formula:
CH ₂ = CR ^Q1- LR ^{Q2
(Wherein, R Q1} is .L represents a hydrogen atom or an alkyl group, a single bond, -CO-O - *, - . The O-CO- * or an -O- * is bonding position of the ^{R Q2} .R ^Q2 representing the a hydrogen atom, and monomers represented by the representative.) the alkyl group or a nitrile group.

Examples of the non-fluoromonomonomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate butyl acrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, vinyl methacrylate, vinyl acetate, acrylic acid, methacrylic acid and acrylonitrile. , Methacrylonitrile, ethyl vinyl ether, cyclohexyl vinyl ether and the like. Of these, butyl methacrylate, vinyl acetate, and acrylic acid are preferable as the non-fluoromonomer.

Examples of the fluoromonomer include perhaloolefins such as HFP, CTFE, and perfluorovinyl ether; fluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms; fluorodioxol and the like. Fluorinated monomer of the ring type; perhaloalkylethylene such as (perfluoroalkyl) ethylene; ω-hydroperhaloolefin; trifluoroethylene, hydrogen-containing fluoroolefin such as vinylidene fluoride [VDF]; perfluoro Examples thereof include allyl ether and the like. The modified monomer can be supplied by initial batch addition or continuous or intermittent partial addition depending on the purpose and the supply of TFE.

The perfluorovinyl ether is not particularly limited, and for example, the following general formula (A): CF ₂ = CF-ORf (A)
(In the formula, Rf represents a perfluoroorganic group.) Examples thereof include perfluorounsaturated compounds represented by. In the present specification, the above-mentioned "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoroorganic group may have ether oxygen.

Examples of the perfluorovinyl ether include perfluoro (alkyl vinyl ether) [PAVE] in which Rf is a perfluoroalkyl group having 1 to 10 carbon atoms in the above general formula (A). The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 5.

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

Further, as the perfluorovinyl ether, in the above general formula (A), Rf is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:

(In the formula, m represents an integer of 0 or 1 to 4), and Rf is the following formula:

(In the formula, n represents an integer of 1 to 4), and the like is a group represented by.

Examples of hydrogen-containing fluoroolefins include CH ₂ = CF ₂ , CFH = CH ₂ , CFH = CF ₂ , CF ₂ = CFCF ₃ , CH ₂ = CFCF ₃ , CH _{2 = CHCF 3} , CHF = CHCF ₃ (E-form), CHF = CHCF ₃ (Z body) and the like can be mentioned.

As the perfluorovinyl ether, at least one selected from the group consisting of perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE) and perfluoro (propyl vinyl ether) (PPVE) is preferable, and PMVE is preferable. More preferred.

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

Examples of perfluoroallyl ether include, for example.
General formula: CF ₂ = CF-CF _2- ORf
(In the formula, Rf represents a perfluoroorganic group.) Examples thereof include fluoromonomers represented by.

The Rf of the above general formula is the same as the Rf of the general formula (A). As Rf, a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms is preferable. Examples of the perfluoroallyl ether include CF ₂ = CF-CF _2- O-CF ₃ , CF ₂ = CF-CF _2- OC ₂ F ₅ , CF ₂ = CF-CF _2- OC ₃ F ₇ . And, at least one selected from the group consisting of _{CF 2} = CF-CF _2- OC ₄ F _{9 is preferable, and CF 2} = CF-CF _2- OC ₂ F ₅ , CF ₂ = CF-CF. _At least one selected from the group consisting of _2- OC ₃ F ₇ and CF ₂ = CF-CF _{2-OC 4} F _{9 is more preferable, and CF 2} = CF-CF _2- O-CF. ₂ CF ₂ CF ₃ is more preferable.

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

Here, the monomer reactivity ratio in the copolymerization with TFE is the rate constant when the growth radical reacts with TFE when the growth radical is less than the repetition unit based on TFE, and the growth radical is a comonomer. It is a value divided by the rate constant when reacting. The lower this value, the higher the reactivity of the comonomer with TFE. The monomer reactivity ratio can be calculated from the Feynman-Loss formula by copolymerizing TFE and comonomer to determine the composition in the produced polymer immediately after the start.

The above copolymerization was carried out using 3600 g of deionized degassed water in an autoclave made of stainless steel having an internal volume of 6.0 L, 1000 mass ppm of ammonium perfluorooctanoate and 100 g of paraffin wax with respect to the water, and the pressure was 0. It is carried out at 78 MPaG and a temperature of 70 ° C. 0.05 g, 0.1 g, 0.2 g, 0.5 g, and 1.0 g of comonomer were added to the reactor, 0.072 g of ammonium persulfate (20 mass ppm against water) was added, and the polymerization pressure was 0.78 MPaG. TFE is continuously supplied in order to maintain. When the TFE charge reaches 1000 g, stirring is stopped and depressurization is performed until the reactor reaches atmospheric pressure. After cooling, the paraffin wax is separated to obtain an aqueous dispersion containing the produced polymer. The aqueous dispersion is stirred to coagulate the resulting polymer and dried at 150 ° C. The composition in the obtained produced polymer is calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

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

（式中、Ｘ^３及びＸ^４はＦ、Ｃｌ又はメトキシ基であり、Ｙは式Ｙ１又はＹ２である。）

(In the formula, X ³ and X ⁴ are F, Cl or methoxy groups, and Y is the formula Y1 or Y2.)

（式Ｙ２中、Ｚ及びＺ’はＦ又は炭素数１〜３のフッ素化アルキル基である。）

(In the formula Y2, Z and Z'are F or a fluorinated alkyl group having 1 to 3 carbon atoms.)

The content of the comonomer (3) unit is preferably in the range of 0.00001 to 1.0% by mass with respect to the total polymerization unit of PTFE. As the lower limit, 0.0001% by mass is more preferable, 0.001% by mass is further preferable, and 0.005% by mass is even more preferable. The upper limit is 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, and 0 in the order of preference. .08% by mass, 0.05% by mass, 0.01% by mass.

As the modified monomer, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, and fluoro (hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, and fluoro () can be obtained as an aqueous dispersion having a small average primary particle diameter, a small aspect ratio of the primary particles, and excellent stability. At least one selected from the group consisting of (alkyl vinyl ether), (perfluoroalkyl) ethylene, ethylene, and a modified monomer having a functional group and a hydrophilic group capable of reacting with radical polymerization is preferable. By using the modified monomer, it is possible to obtain an aqueous dispersion of PTFE having a smaller average primary particle size, a smaller aspect ratio of the primary particles, and excellent dispersion stability.

From the viewpoint of reactivity with TFE, the modified monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro (alkyl vinyl ether) and (perfluoroalkyl) ethylene.
More preferably, it is selected from the group consisting of hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), (perfluorobutyl) ethylene, (perfluorohexyl) ethylene, and (perfluorooctyl) ethylene. Is to include at least one species.
The total amount of the hexafluoropropylene unit, the perfluoro (alkyl vinyl ether) unit and the (perfluoroalkyl) ethylene unit may be in the range of 0.00001 to 1.0% by mass with respect to the total polymerization unit of PTFE. preferable. As the lower limit of the total amount, 0.0001% by mass is more preferable, 0.001% by mass is further preferable, and 0.005% by mass is further preferable. The upper limit is 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, and 0 in the order of preference. .08% by mass, 0.05% by mass, 0.01% by mass.

It is also preferable that the modified monomer contains a modified monomer having a functional group and a hydrophilic group capable of reacting by radical polymerization (hereinafter referred to as "modified monomer (A)").

By the presence of the modified monomer (A), PTFE particles having a small primary particle size can be obtained, and an aqueous dispersion having high dispersion stability can be obtained. In addition, the aspect ratio of the primary particles can be reduced.

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

Since the modified monomer (A) is highly water-soluble, even if the unreacted modified monomer (A) remains in the aqueous dispersion, it can be easily removed in the concentration step or the coagulation / washing step.

The modified monomer (A) is incorporated into the produced polymer in the process of polymerization, but the concentration of the modified monomer (A) in the polymerization system itself is low and the amount incorporated into the polymer is small, so that the heat resistance of PTFE is lowered. There is no problem of coloring after baking.

Examples of the hydrophilic group in the modified monomer (A) include -NH ₂ , -PO ₃ M, -P (O) (OM) ₂ , -OPO ₃ M, -OP (O) (OM) ₂ , and -SO. in _{3 M, -OSO 3 M, -COOM} ( each formula, M represents, H, a metal atom, ^NR _{7 4,} which may imidazolium substituted, pyridinium which may have a substituent or which may have a substituent phosphonium, R ⁷ is H or an organic group and may be the same or different. bonded to any two Tsugaotagai, may form a ring.) is Can be mentioned. As the hydrophilic group, -SO ₃ M or -COOM is particularly preferable. As ^{the organic group of R 7} , an alkyl group is preferable. As R ⁷ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, and an alkyl group of _{H or C 1-4 is further preferable.}
Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable.

Examples of the "functional group capable of reacting by radical polymerization" in the modified monomer (A) include groups having an ethylenically unsaturated bond such as a vinyl group and an allylic group. The group having an ethylenically unsaturated bond has the following formula:
CX ^e X ^g = CX ^f R-
(In the formula, X ^e , X ^f and X ^g are independently F, Cl, H, CF ₃ , CF ₂ H, CFH ₂ or CH ₃ ; R is a linking group). Can be indicated by. The linking group R include linking groups as R ^a, which will be described later. Preferably -CH = CH ₂ , -CF = CH _2, -CH = CF _2, -CF = CF ₂ , -CH ₂ -CH = CH ₂ , -CF ₂ -CF = CH ₂ , -CF ₂ -CF = CF ₂ ,-(C = O) -CH = CH ₂ ,-(C = O) -CF = CH ₂ ,-(C = O) -CH = CF ₂ ,-(C = O) -CF = CF ₂ ,-(C = O) -C (CH ₃ ) = CH ₂ ,-(C = O) -C (CF ₃ ) = CH ₂ ,-(C = O) -C (CH ₃ ) = CF ₂ ,- (C = O) -C (CF ₃ ) = CF ₂ , -O-CH ₂ -CH = CH ₂ , -O-CF ₂ -CF = CH ₂ , -O-CH ₂ -CH = CF ₂ , -O Examples include groups having unsaturated bonds such as _{−CF 2} −CF = CF _2.

Since the modified monomer (A) has a functional group capable of reacting by radical polymerization, when used in the polymerization, it reacts with TFE at the initial stage of the polymerization reaction and has a hydrophilic group derived from the modified monomer (A) and is stable. It is presumed that highly potent particles are formed. Therefore, it is considered that the number of particles increases when the polymerization is carried out in the presence of the modified monomer (A).

In the polymerization, one kind of the modified monomer (A) may be present, or two or more kinds of the modified monomer (A) may be present.

In the polymerization, a compound having an unsaturated bond can be used as the modified monomer (A).

The modified monomer (A) has a general formula (4):
CX ⁱ X ^k = CX ^j R ^a- (CZ ¹ Z ² ) _k- Y ³ (4)
(In the formula, X ⁱ , X ^j and X ^k are independently F, Cl, H or CF ₃ ; Y ³ is a hydrophilic group; ^Ra is a linking group; Z ¹ and Z ² is independently H, F or CF ₃ , and k is preferably 0 or 1).
Examples of the hydrophilic group include -NH ₂ , -PO ₃ M, -P (O) (OM) ₂ , -OPO ₃ M, -OP (O) (OM) ₂ , -SO ₃ M, and -OSO _3. M, in -COOM (each formula, M represents, H, a metal atom, NR 7 _^4, which may imidazolium substituted, have good pyridinium or substituted group which may have a substituent good phosphonium be, R ⁷ is H or an organic group and may be the same or different. bonded to any two Tsugaotagai, may form a ring.) it can be mentioned. As the hydrophilic group, -SO ₃ M or -COOM is particularly preferable. As ^{the organic group of R 7} , an alkyl group is preferable. As R ⁷ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, and an alkyl group of _{H or C 1-4 is further preferable.}
Examples of the metal atom include 1,2-valent metal atoms, alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li are preferable.
By using the modified monomer (A), an aqueous dispersion having a smaller average primary particle size and more excellent stability can be obtained. It is also possible to make the aspect ratio of the primary particles smaller.

The ^Ra is a linking group. As used herein, the term "linking group" refers to a divalent linking group. The linking group may be a single bond and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, or 8 or more. It may be 10 or more, and may be 20 or more. The upper limit is not limited, but may be 100 or less, and may be 50 or less, for example.
The linking group may be chain or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and may optionally be one or more selected from the group consisting of sulfur, oxygen, and nitrogen. It may contain a heteroatom and optionally contain one or more functional groups selected from the group consisting of esters, amides, sulfone amides, carbonyls, carbonates, urethanes, ureas and carbamate. The linking group does not contain a carbon atom and may be a catenary heteroatom such as oxygen, sulfur or nitrogen.

The ^Ra is preferably a catenary heteroatom such as oxygen, sulfur or nitrogen, or a divalent organic group.
When Ra is ^a divalent organic group, the hydrogen atom bonded to the carbon atom may be replaced with a halogen other than fluorine, for example, chlorine, and may or may not contain a double bond. Furthermore, R ^a is linear and may be either branched, may be either cyclic or acyclic. Further, ^Ra may contain a functional group (for example, an ester, an ether, a ketone, an amine, a halide, etc.).
^Ra may also be a non-fluorinated divalent organic group or a partially fluorinated or perfluorinated divalent organic group.
^{Examples of Ra} include a hydrocarbon group in which a fluorine atom is not bonded to a carbon atom, a hydrocarbon group in which a part of the hydrogen atom bonded to the carbon atom is replaced with a fluorine atom, and a hydrogen atom bonded to the carbon atom. It may be a hydrocarbon group containing a hydrocarbon group entirely substituted with a fluorine atom,-(C = O)-,-(C = O) -O-, or-(C = O)-. , These may contain oxygen atoms, may contain double bonds, and may contain functional groups.

^Ra may contain a-(C = O)-,-(C = O) -O-, or an ether bond, and may contain a carbonyl group. A hydrocarbon group having 1 to 100 carbon atoms. In the hydrocarbon group, a part or all of the hydrogen atom bonded to the carbon atom may be substituted with fluorine.
Preferred as R ^a are-(CH ₂ ) _a -,-(CF ₂ ) _a- , -O- (CF ₂ ) _a -,-(CF ₂ ) _a- O- (CF ₂ ) _{b-, -O.} (CF ₂ ) _a −O − (CF ₂ ) _b −, − (CF ₂ ) _a − [O − (CF ₂ ) _b ] _c −, _{−O (CF 2} ) _a − [O − (CF ₂ ) _b ] _C -,-[(CF ₂ ) _a- O] _b -[(CF ₂ ) _c- O] _d- , -O [(CF ₂ ) _a- O] _b -[(CF ₂ ) _c- O] _d- , -O- [CF ₂ CF (CF ₃ ) O] _a- (CF ₂ ) _b -,-(C = O)-,-(C = O) -O-,-(C = O)- (CH ₂ ) _a -,-(C = O)-(CF ₂ ) _a -,-(C = O) -O- (CH ₂ ) _a -,-(C = O) -O- (CF ₂ ) _a -,-(C = O)-[(CH ₂ ) _a- O] _b -,-(C = O)-[(CF ₂ ) _a- O] _b -,-(C = O) -O [ (CH ₂ ) _a- O] _b -,-(C = O) -O [(CF ₂ ) _a- O] _b -,-(C = O) -O [(CH ₂ ) _a- O] _b- (CH ₂ ) _c −, − (C = O) −O [(CF ₂ ) _a −O] _b − (CF ₂ ) _c −, − (C = O) − (CH ₂ ) _a −O− (CH) ₂ ) _b -,-(C = O)-(CF ₂ ) _a- O- (CF ₂ ) _b -,-(C = O) -O- (CH ₂ ) _a- O- (CH ₂ ) _{b- , - (C = O) -O-} (CF 2) a -O- (CF 2) b -, - (C = O) -O-C 6 H 4 -, and, at least is selected from these combinations It is one kind.
In the formula, a, b, c and d are independently at least one or more. a, b, c and d may be independently 2 or more, 3 or more, 4 or more, 10 or more, and 20 or more. The upper limit of a, b, c and d is, for example, 100.

As preferable specific examples of R ^a _{are, -CF 2 -O -, - CF} 2 -O-CF 2 -, - CF 2 -O-CH 2 -, - CF 2 -O-CH 2 CF 2 -, - CF _2- O-CF ₂ CF _2- , -CF _2- O-CF ₂ CH _2- , -CF _2- O-CF ₂ CF ₂ CH _2- , -CF _2- O-CF (CF ₃ )-, _{-CF 2 -O-CF (CF 3} ) CF 2 -, - CF 2 -O-CF (CF 3) CF 2 -O -, - CF 2 -O-CF (CF 3) CH 2 -, - (C = O)-,-(C = O) -O-,-(C = O)-(CH ₂ )-,-(C = O)-(CF ₂ )-,-(C = O) -O- (CH ₂ )-,-(C = O) -O- (CF ₂ )-,-(C = O)-[(CH ₂ ) _2- O] _n -,-(C = O)-[(CF) ₂ ) ₂ −O] _n −, − (C = O) −O [(CH ₂ ) ₂ −O] _n −, − (C = O) −O [(CF ₂ ) ₂ −O] _n −, − (C = O) -O [(CH ₂ ) _2- O] _n- (CH ₂ )-,-(C = O) -O [(CF ₂ ) _2- O] _n- (CF ₂ )-,- (C = O)-(CH ₂ ) _2- O- (CH ₂ )-,-(C = O)-(CF ₂ ) _2- O- (CF ₂ )-,-(C = O) -O- (CH ₂ ) _2- O- (CH ₂ )-,-(C = O) -O- (CF ₂ ) _2- O- (CF ₂ )-,-(C = O) -O-C ₆ H ₄ -Etc. Of these, the ^{R a} is _{specifically, -CF 2 -O -, - CF} 2 -O-CF 2 -, - CF 2 -O-CF 2 CF 2 -, - CF 2 -O-CF (CF ₃ )-, -CF _2- O-CF (CF ₃ ) CF _2- , -CF _2- O-CF (CF ₃ ) CF _2- O-,-(C = O)-,-(C = O) -O-,-(C = O)-(CH ₂ )-,-(C = O) -O- (CH ₂ )-,-(C = O) -O [(CH ₂ ) ₂ -O] _n −, − (C = O) −O [(CH ₂ ) ₂ −O] _n − (CH ₂ ) −, − (C = O) − (CH ₂ ) ₂ −O − (CH ₂ ) −, or _{- (C = O) -O-} C 6 H 4 - it is preferred.
In the above formula, n is an integer of 1 to 10.

^{As −R a} − (CZ ¹ Z ² ) _k − in the above general formula (4), −CF ₂ −O − CF ₂ −, _{−CF 2} −O−CF (CF ₃ ) −, −CF ₂ −O _{-C (CF 3) 2 -,} - CF 2 -O-CF 2 -CF 2 -, - CF 2 -O-CF 2 -CF (CF 3) -, - CF 2 -O-CF 2 -C (CF _{3) 2 -, - CF 2} -O-CF 2 CF 2 -CF 2 -, - CF 2 -O-CF 2 CF 2 -CF (CF 3) -, - CF 2 -O-CF 2 CF 2 -C _{(CF 3) 2 -, -} CF 2 -O-CF (CF 3) -CF 2 -, - CF 2 -O-CF (CF 3) -CF (CF 3) -, - CF 2 -O-CF ( _{CF 3) -C (CF 3)} 2 -, - CF 2 -O-CF (CF 3) -CF 2 -, - CF 2 -O-CF (CF 3) -CF (CF 3) -, - CF 2 _{-O-CF (CF 3) -C} (CF 3) 2 -, - CF 2 -O-CF (CF 3) CF 2 -CF 2 -, - CF 2 -O-CF (CF 3) CF 2 -CF (CF ₃ )-, -CF _2- O-CF (CF ₃ ) CF _2- C (CF ₃ ) _2- , -CF _2- O-CF (CF ₃ ) CF _2- O-CF _2- , -CF _2- O-CF (CF ₃ ) CF _2- O-CF (CF ₃ )-, -CF _2- O-CF (CF ₃ ) CF _2- OC (CF ₃ ) ₂ -,-(C = O) )-,-(C = O) -O-,-(C = O)-(CH ₂ )-,-(C = O)-(CF ₂ )-,-(C = O) -O- (CH) ₂ )-,-(C = O) -O- (CF ₂ )-,-(C = O)-[(CH ₂ ) _2- O] _n- (CH ₂ )-,-(C = O)- [(CF ₂ ) ₂ −O] _n − (CF ₂ ) −, − (C = O) − [(CH ₂ ) ₂ −O] _n − (CH ₂ ) − (CH ₂ ) −, − (C = O)-[(CF ₂ ) _2- O] _n- (CF ₂ )-(CF ₂ )-,-(C = O) -O [(CH ₂ ) _2- O] _n- (CF ₂ )-, − (C = O) −O [(CH ₂ ) ₂ −O] _n − (CH ₂ ) − (CH ₂ ) −, − (C = O) −O [(CF ₂ ) ₂ −O] _n − ( CF ₂ ) -,-(C = O) -O [(CF ₂ ) ₂ -O] _n- (CF ₂ )-(CF ₂ )-,-(C = O)-(CH ₂ ) _2- O- (CH ₂₎ )-(CH ₂ )-,-(C = O)-(CF ₂ ) _2- O- (CF ₂ )-(CF ₂ )-,-(C = O) -O- (CH ₂ ) _2- O -(CH ₂ )-(CH ₂ )-,-(C = O) -O- (CF ₂ ) _2- O- (CF ₂ )-(CF ₂ )-,-(C = O) -O- ( CH ₂ ) _2- O- (CH ₂ ) -C (CF ₃ ) ₂ -,-(C = O) -O- (CF ₂ ) _2- O- (CF ₂ ) -C (CF ₃ ) _2- , Alternatively,-(C = O) -O-C ₆ H _4- C (CF ₃ ) _2- is preferable, and -CF _2- O-CF (CF ₃ )-, -CF _2- O-CF _{2-CF (} CF ₃ )-, _{-CF 2-} O-CF ₂ CF ₂ -CF (CF ₃ )-, _{-CF 2-} O-CF (CF ₃ ) -CF (CF ₃ )-, _{-CF 2-} O-CF ( CF ₃ ) CF _2- CF (CF ₃ )-, _{-CF 2-} O-CF (CF ₃ ) CF _2- O-CF (CF ₃ )-,-(C = O)-,-(C = O) -O- (CH ₂ )-,-(C = O) -O- (CH ₂ )-(CH ₂ )-,-(C = O) -O [(CH ₂ ) ₂ -O] _n- (CH) ₂ )-(CH ₂ )-,-(C = O) -O- (CH ₂ ) _2- O- (CH ₂ ) -C (CF ₃ ) _2- or-(C = O) -O- C ₆ H _4- C (CF ₃ ) _2- is more preferable.
In the above formula, n is an integer of 1 to 10.

（式中、Ｘ^ｊ及びＹ^３は上記と同じ。ｎは１〜１０の整数である。）等が挙げられる。Specific examples of the compound represented by the general formula (4) include

(In the formula, X ^j and Y ³ are the same as above. N is an integer of 1 to 10.) And the like.

As R ^a , the following general formula (r1):
-(C = O) _h- (O) _{i -CF 2-} O- (CX ⁶ ₂ ) _e- {O-CF (CF ₃ )} _f- (O) _g- (r1)
(In the equation, X ⁶ is H, F or CF ₃ independently, e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, and h is. A divalent group represented by (0 or 1 and i is 0 or 1) is preferable, and the following general formula (r2):
-(C = O) _h- (O) _{i- CF 2-} O- (CX ⁷ ₂ ) _e- (O) _g- (r2) (In the formula, X ⁷ is H, F or CF _{3 independently.} A divalent group represented by (e is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1) is also preferred.

^{As the −R a} − (CZ ¹ Z ² ) _k − of the above general formula (4), the following formula (t1):
^{_{- (C = O) h -}} (O) i -CF 2 -O- (CX 6 2) e - {O-CF (CF 3)} f - (O) g -CZ 1 Z 2 - (t1)
(In the equation, X ⁶ is H, F or CF ₃ independently, e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, and h is. A divalent group represented by (0 or 1), i is 0 or 1, and Z ¹ and Z ² are independently F or CF ₃ ) is also preferred, and in formula (t1). It is more preferable that Z ¹ and Z ² are F on one side and CF _{3 on the other side.}
Further, in the above general formula (4), as −R ^a − (CZ ¹ Z ² ) _k −, the following formula (t2):
-(C = O) _h- (O) _{i -CF 2-} O- (CX ⁷ ₂ ) _e- (O) _g- CZ ¹ Z ^2- (t2)
(In the equation, X ⁷ is independently H, F or CF ₃ , e is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or. is 1, ^{Z 1} and ^{Z 2} are each independently, also preferably a divalent group represented by F or CF is _3), in the formula (t2), ^{Z 1} and ^{Z 2,} one F It is more preferable that the other is CF _3.

It is also preferable that the compound represented by the general formula (4) has a CF bond and does not have a CH bond, except for the ^{hydrophilic group (Y 3).} That is, in the general formula (4), all of X ⁱ , X ^j , and X ^k are F, and ^Ra is preferably a perfluoroalkylene group having 1 or more carbon atoms, and the perfluoroalkylene group is preferably a perfluoroalkylene group. , Chained or branched, cyclic or acyclic, and may contain at least one catenary heteroatom. The perfluoroalkylene group may have 2 to 20 carbon atoms and may have 4 to 18 carbon atoms.

The compound represented by the general formula (4) may be partially fluorinated. That is, the compound represented by the general formula (4) has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom, except for the ^{hydrophilic group (Y 3).} It is also preferable.

The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4a).
CF ₂ = CF-O-Rf ^0- Y ³ (4a)
(In the formula, Y ³ is a hydrophilic group and Rf ⁰ is hyperfluorinated and may be chain or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted. It is a perfluorinated divalent linking group that optionally additionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.)

The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4b).
CH ₂ = CH-O-Rf ^0- Y ³ (4b)
(In the formula, Y ³ is a hydrophilic group and Rf ⁰ is a perfluorinated divalent linking group defined by the formula (4a).)

In the general formula (4), Y ³ is one of the preferable forms of _{−OSO 3 M.} When Y ³ is −OSO ₃ M, the compounds represented by the general formula (4) include CF ₂ = CF (OCF ₂ CF ₂ CH ₂ OSO ₃ M) and CH ₂ = CH ((CF _{2 ) 4} ). CH ₂ OSO ₃ M), CF ₂ = CF (O (CF ₂ ) ₄ CH ₂ OSO ₃ M), CF ₂ = CF (OCF ₂ CF (CF ₃ ) CH ₂ OSO ₃ M), CF ₂ = CF (OCF) ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ OSO ₃ M), CH ₂ = CH ((CF ₂ ) ₄ CH ₂ OSO ₃ M), CF ₂ = CF (OCF ₂ CF ₂ SO ₂ N (CH ₃ )) CH ₂ CH ₂ OSO ₃ M), CH ₂ = CH (CF ₂ CF ₂ CH ₂ OSO ₃ M), CF ₂ = CF (OCF ₂ CF ₂ CF ₂ CF ₂ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OSO ₃ M), CH ₂ = CH (CF ₂ CF ₂ CH ₂ OSO ₃ M) and the like. In the above formula, M is the same as above.

In the general formula (4), it is also one of the preferable forms that ^{Y 3} is −SO _{3 M.} When Y ³ is −SO ₃ M, the compounds represented by the general formula (4) include CF ₂ = CF (OCF ₂ CF ₂ SO ₃ M) and CF ₂ = CF (O (CF _{2 ) 4} SO). ₃ M), CF ₂ = CF (OCF ₂ CF (CF ₃ ) SO ₃ M), CF ₂ = CF (OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ M), CH ₂ = CH (CF ₂ CF) ₂ SO ₃ M), CF ₂ = CF (OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ SO ₃ M), CH ₂ = CH ((CF ₂ ) ₄ SO ₃ M), CH ₂ = CH (CF ₂ CF ₂ SO ₃ M), CH ₂ = CH ((CF ₂ ) ₃ SO ₃ M) and the like can be mentioned. In the above formula, M is the same as above.

In the general formula (4), it is also one of the preferable forms that ^{Y 3 is −COMM.} When Y ³ is −COOM, the compounds represented by the general formula (4) include CF ₂ = CF (OCF ₂ CF ₂ COOM), CF ₂ = CF (OCF ₂ CF ₂ CF ₂ COOM), and CF ₂ = CF (O (CF ₂ ) ₅ COM), CF ₂ = CF (OCF ₂ CF (CF ₃ ) COM), CF ₂ = CF (OCF ₂ CF (CF ₃ ) O (CF ₂ ) _n COM) (n is (Greater than 1), CH ₂ = CH (CF ₂ CF ₂ COM), CH ₂ = CH ((CF ₂ ) ₄ COM), CH ₂ = CH (CF ₂ CF ₂ COM), CH ₂ = CH ((CF _{2) 4 COM) ) 3 COOM), CF 2 =} CF (OCF 2 CF 2 SO 2 NR'CH 2 COOM), CF 2 = CF (O (CF 2) 4 SO 2 NR'CH 2 COOM), CF 2 = CF (OCF 2 _{CF (CF 3) SO 2 NR'CH} 2 COOM), CF 2 = CF (OCF 2 CF (CF 3) OCF 2 CF 2 SO 2 NR'CH 2 COOM), CH 2 = CH (CF 2 CF 2 SO 2 NR'CH ₂ COM), CF ₂ = CF (OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ CF ₂ SO ₂ NR'CH ₂ COM), CH ₂ = CH ((CF ₂ ) ₄ SO ₂ NR' CH ₂ COM), CH ₂ = CH (CF ₂ CF ₂ SO ₂ NR'CH ₂ COM), CH ₂ = CH ((CF ₂ ) ₃ SO ₂ NR'CH ₂ COM) and the like. In the above formula, _R'is an H or C 1-4 alkyl group, and M is the same as above.

In the general formula (4), it is also one of the preferable forms that ^{Y 3} is −OPO ₃ M or −OP (O) (OM) _2. When Y ³ is -OPO ₃ M or -OP (O) (OM) ₂ , the compound represented by the general formula (4) is CF ₂ = CF (OCF ₂ CF ₂ CH ₂ OP (O) (O) ( OM) ₂ ), CF ₂ = CF (O (CF ₂ ) ₄ CH ₂ OP (O) (OM) ₂ ), CF ₂ = CF (OCF ₂ CF (CF ₃ ) CH ₂ OP (O) (OM) ₂ ), CF ₂ = CF (OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ OP (O) (OM) ₂ ), CF ₂ = CF (OCF ₂ CF ₂ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OP (O) (OM) ₂ ), CF ₂ = CF (OCF ₂ CF ₂ CF ₂ CF ₂ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OP (O) (OM) ₂ ), CH ₂ = CH (CF) ₂ CF ₂ CH ₂ OP (O) (OM) ₂ , CH ₂ = CH ((CF ₂ ) ₄ CH ₂ OP (O) (OM) ₂ ), CH ₂ = CH (CF ₂ CF ₂ CH ₂ OP (O) ) (OM) ₂ ), CH ₂ = CH ((CF ₂ ) ₃ CH ₂ OP (O) (OM) ₂ ), etc. In the above formula, M is the same as above.

In the general formula (4), it is also one of the preferable forms that ^{Y 3} is −PO ₃ M or −P (O) (OM) _2. When Y ³ is −PO ₃ M or −P (O) (OM) ₂ , the compound represented by the general formula (4) is CF ₂ = CF (OCF ₂ CF ₂ P (O) (OM). ₂ ), CF ₂ = CF (O (CF ₂ ) ₄ P (O) (OM) ₂ ), CF ₂ = CF (OCF ₂ CF (CF ₃ ) P (O) (OM) ₂ ), CF ₂ = CF (OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ P (O) (OM) ₂ ), CH ₂ = CH (CF ₂ CF ₂ P (O) (OM) ₂ ), CH ₂ = CH ((CF ₂ )) ₄ P (O) (OM) ₂ ), CH ₂ = CH (CF ₂ CF ₂ P (O) (OM) ₂ ), CH ₂ = CH ((CF ₂ ) ₃ P (O) (OM) ₂ ) In the formula, M is the same as above.

Examples of the compound represented by the above general formula (4) include the following general formula (5) :.
CX ₂ = CY (-CZ _2- O-Rf-Y ³ ) (5)
(In the formula, X is the same or different, −H or −F, Y is −H, −F, an alkyl group or a fluorine-containing alkyl group, and Z is the same or different, −H, −. F, alkyl group or fluorine-containing alkyl a group .Rf the fluorine-containing alkylene group having 1 to 40 carbon atoms, or, .Y ³ is a fluorine-containing alkylene group having ether bond having 2-100 carbon atoms, said a The same monomer represented by), the following general formula (6) :.
CX ₂ = CY (-O-Rf-Y ³ ) (6)
(In the formula, X is the same or different, −H or −F, Y is −H, −F, an alkyl group or a fluorine-containing alkyl group, and Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms. or, .Y ³ is a fluorine-containing alkylene group having ether bond having 2-100 carbon atoms is a monomer represented by the same as) and the following general formula (7).:
CX ₂ = CY (-Rf-Y ³ ) (7)
(In the formula, X is the same or different, −H or −F, Y is −H, −F, an alkyl group or a fluorine-containing alkyl group, and Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms. or, .Y ³ is a fluorine-containing alkylene group having ether bond having 2-100 carbon atoms are the same as defined above, and. the monomer represented by), at least one selected from the group consisting of It is preferable to have.
The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is a terminal and contains an ether bond between carbon carbons.

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

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

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

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

In the general formula (5), the Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
The fluorine-containing alkylene group preferably has 2 or more carbon atoms. Further, 30 or less is preferable, 20 or less is more preferable, and 10 or less is further preferable. As the fluorinated alkylene _{group, -CF 2 -, - CH 2} CF 2 -, - CF 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 CH 2 -, - CF (CF 3) - _{, -CF (CF 3) CF 2} -, - CF (CF 3) CH 2 - and the like. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

（式中、Ｚ^１はＦまたはＣＦ_３；Ｚ^２及びＺ^３はそれぞれＨまたはＦ；Ｚ^４はＨ、ＦまたはＣＦ_３；ｐ１＋ｑ１＋ｒ１が１〜１０の整数；ｓ１は０または１；ｔ１は０〜５の整数）で表される２価の基であることも好ましい。
上記エーテル結合を有する含フッ素アルキレン基として具体的には、−ＣＦ（ＣＦ_３）ＣＦ_２−Ｏ−ＣＦ（ＣＦ_３）−、−（ＣＦ（ＣＦ_３）ＣＦ_２−Ｏ）_ｎ−ＣＦ（ＣＦ_３）−（式中、ｎは１〜１０の整数）、−ＣＦ（ＣＦ_３）ＣＦ_２−Ｏ−ＣＦ（ＣＦ_３）ＣＨ_２−、−（ＣＦ（ＣＦ_３）ＣＦ_２−Ｏ）_ｎ−ＣＦ（ＣＦ_３）ＣＨ_２−（式中、ｎは１〜１０の整数）、−ＣＨ_２ＣＦ_２ＣＦ_２Ｏ−ＣＨ_２ＣＦ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２ＣＦ_２Ｏ−ＣＦ_２ＣＦ_２−、−ＣＦ_２ＣＦ_２ＣＦ_２Ｏ−ＣＦ_２ＣＦ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２Ｏ−ＣＦ_２−、−ＣＦ_２ＣＦ_２Ｏ−ＣＦ_２ＣＨ_２−等が挙げられる。上記エーテル結合を有する含フッ素アルキレン基は、パーフルオロアルキレン基であることが好ましい。The fluorine-containing alkylene group having an ether bond preferably has 3 or more carbon atoms. The carbon number of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, still more preferably 12 or less.
Examples of the fluorine-containing alkylene group having an ether bond include the following formula:

(In the formula, Z ¹ is F or CF ₃ ; Z ² and Z ³ are H or F, respectively; Z ⁴ is H, F or CF ₃ ; p1 + q1 + r1 is an integer of 1 to 10; s1 is 0 or 1; t1 is 0. It is also preferable that it is a divalent group represented by (an integer of ~ 5).
Specific examples of the fluorine-containing alkylene group having an ether bond include -CF (CF ₃ ) CF _2- O-CF (CF ₃ )-,-(CF (CF ₃ ) CF _2- O) _{n-CF (CF). 3} )-(In the formula, n is an integer of 1 to 10), -CF (CF ₃ ) CF _2- O-CF (CF ₃ ) CH ₂ -,-(CF (CF ₃ ) CF _2- O) _n- CF (CF ₃ ) CH _2- (in the formula, n is an integer of 1 to 10), -CH ₂ CF ₂ CF ₂ O-CH ₂ CF ₂ CH _2- , -CF ₂ CF ₂ CF ₂ O-CF ₂ CF _2- , -CF ₂ CF ₂ CF ₂ O-CF ₂ CF ₂ CH _2- , -CF ₂ CF ₂ O-CF _2- , -CF ₂ CF ₂ O-CF ₂ CH _2- and the like can be mentioned. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

In the general formula ^{(5), Y} 3 is, -COOM, -SO ₃ M or -OSO ₃ M (M is, H, a metal atom, ^NR _{7 4,} good imidazolium be substituted, substituted good phosphonium have a good pyridinium or substituted group which may have a group, R ⁷ is H or an organic group and may be the same or different. bonded to any two Tsugaotagai, A ring may be formed.).
As ^{the organic group of R 7} , an alkyl group is preferable. As R ⁷ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, and an alkyl group of _{H or C 1-4 is further preferable.}
Examples of the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2) and the like, and Na, K or Li are preferable.
As the M, -H, preferably is a metal atom or ^-NR _{7 4,} -H, alkali metal (Group 1), alkaline earth metal (Group 2) or ^-NR _{7 4,} more preferably, -H, -Na , -K, -Li or -NH ₄ are more preferable, -Na, preferably from -K or -NH ₄ further particularly preferred -Na or -NH _4, -NH ₄ is most preferred.
As the above Y ³ , -COOM or -SO ₃ M is preferable, and -COOM is more preferable.

The monomer represented by the general formula (5) is preferably the monomer (5a) represented by the following general formula (5a).
CH ₂ = CF (-CF _2- O-Rf-Y ³ ) (5a)
(Wherein, Rf and ^{Y 3} are as defined above.)

Specifically, as the monomer represented by the general formula (5a), the following formula is used.

(In the equation, Z ¹ is F or CF ₃ ; Z ² and Z ³ are H or F, respectively; Z ⁴ is H, F or CF ₃ ; p1 + q1 + r1 is an integer of 0 to 10; s1 is 0 or 1; t1 is 0. The integer of ~ 5, Y ³ is the same as above. However, when Z ³ and Z ⁴ are both H, p1 + q1 + r1 + s1 is not 0). More specifically

Etc. are preferred, especially

Is preferable.

As the monomer represented by the general formula (5a), ^{it is preferable that Y 3} in the formula (5a) is −COOM, and in particular, CH ₂ = CFCF ₂ OCF (CF ₃ ) COOM and CH. _At least one selected from the group consisting of 2 = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COM (where M is the same as defined above) is preferred, and CH ₂ = CFCF ₂ OCF (CF). ₃ ) COM is more preferable.

The monomer represented by the general formula (5) is preferably the monomer (5b) represented by the following general formula (5b).
CX ² ₂ = CFCF _2- O- (CF (CF ₃ ) CF ₂ O) _n5- CF (CF ₃ ) -Y ³
(5b)
(In the equation, each X ² is the same and represents F or H. N5 represents an integer of 0 or 1-10, and Y ³ is the same as the above definition.)

In the above formula (5b), the above n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1 or 2, and 0 or 1 in terms of the stability of the obtained aqueous dispersion. Is more preferable. The Y ³ is preferably -COOM from the stability of the proper water solubility and an aqueous dispersion is obtained, the M is less likely to remain as an impurity, the heat resistance of the obtained molded article is improved In terms of points, it is preferably _{H or NH 4.}

Examples of the monomer represented by the above formula (5b) include CH ₂ = CFCF ₂ OCF (CF ₃ ) COM, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COM (in the formula). , M is the same as the above definition.).

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

CF ₂ = CFCF _2- O-Rf-Y ³ (5c)
(Wherein, Rf and ^{Y 3} are as defined above)

等が挙げられる。More specifically

And so on.

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

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

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

In the general formula (6), the Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
The fluorine-containing alkylene group preferably has 2 or more carbon atoms. The number of carbon atoms of the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less. As the fluorinated alkylene _{group, -CF 2 -, - CH 2} CF 2 -, - CF 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 CH 2 -, - CF (CF 3) - _{, -CF (CF 3) CF 2} -, - CF (CF 3) CH 2 - and the like. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

In the general formula ^{(6), Y} 3 is, -COOM, -SO ₃ M or -OSO ₃ M (M is, H, a metal atom, ^NR _{7 4,} good imidazolium be substituted, substituted good phosphonium have a good pyridinium or substituted group which may have a group, R ⁷ is H or an organic group and may be the same or different. bonded to any two Tsugaotagai, A ring may be formed.).
As ^{the organic group of R 7} , an alkyl group is preferable. As R ⁷ , an organic group of H or C _1-10 is preferable, an organic group of H or C _1-4 is more preferable, and an alkyl group of _{H or C 1-4 is further preferable.}
Examples of the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2) and the like, and Na, K or Li are preferable.
As the M, -H, preferably is a metal atom or ^-NR _{7 4,} -H, alkali metal (Group 1), alkaline earth metal (Group 2) or ^-NR _{7 4,} more preferably, -H, -Na , -K, -Li or -NH ₄ are more preferable, -Na, preferably from -K or -NH ₄ further particularly preferred -Na or -NH _4, -NH ₄ is most preferred.
As the above Y ³ , -COOM or -SO ₃ M is preferable, and -COOM is more preferable.

The monomer represented by the general formula (6) is selected from the group consisting of the monomers represented by the following general formulas (6a), (6b), (6c), (6d) and (6e). At least one type is preferable.
CF ₂ = CF-O- (CF ₂ ) _n1- Y ³ (6a)
(Wherein, n1 represents an integer of 1 to 10, ^{Y 3} is as previously defined.)
CF ₂ = CF-O- (CF ₂ C (CF ₃ ) F) _n2- Y ³ (6b)
(Wherein, n2 represents an integer of 1 to 5, ^{Y 3} is as previously defined.)
^{_{CF 2 = CF-O- (CFX}} 1) n3 -Y 3 (6c)
(In the equation, X ¹ represents F or CF ₃ , n 3 represents an integer of 1 to 10, and Y ³ is the same as the above definition.)
CF ₂ = CF-O- (CF ₂ CFX ¹ O) _n4- (CF ₂ ) _n6- Y ³ (6d)
(In the formula, n4 represents an integer of 1 to 10, n6 represents an integer of ^{1 to 3,} and Y 3 and X 1 are the same as the above definitions.)
^{_{CF 2 = CF-O- (CF}} 2 CF 2 CFX 1 O) n5 -CF 2 CF 2 CF 2 -Y 3 (6e)
(Wherein, the n5, represents an integer of 0, ^{Y 3} and ^{X 1} are as previously defined.)

In the above formula (6a), the above n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. The Y ³ are points obtained stability proper water solubility and an aqueous dispersion is preferably -COOM, M is little tendency toward remaining as an impurity, that the heat resistance of the resulting molded article is improved Therefore, it is preferably H or NH _4.

Examples of the monomer represented by the above formula (6a) include CF ₂ = CF-O-CF ₂ COOM, CF ₂ = CF (OCF ₂ CF ₂ COOM), and CF ₂ = CF (OCF ₂ CF ₂ CF). ₂ COMM) (in the formula, M is the same as the above definition).

In the above formula (6b), said n2 is in terms of stability of the resulting aqueous dispersion is preferably 3 or less an integer, Y ³ is the stability of the proper water solubility and an aqueous dispersion obtained In that respect, it is preferably −COOM, and M is preferably H or NH ₄ in that it does not easily remain as an impurity and the heat resistance of the obtained molded product is improved.

In the above formula (6c), said n3 is preferably 5 or less integer in terms of water-soluble, the Y ³ is in that the stability of the proper water solubility and an aqueous dispersion is obtained, -COOM The above M is preferably H or NH ₄ in that the dispersion stability is improved.

In the above formula (6d), the above X ¹ _{is preferably −CF 3} in terms of the stability of the aqueous dispersion, and the above n4 is preferably an integer of 5 or less in terms of water solubility. the Y ³ is preferably -COOM from the stability of the proper water solubility and an aqueous dispersion is obtained, the M is preferably H or NH _4.

Examples of the monomer represented by the above formula (6d) include CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOM, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ COOM, CF ₂ =. CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ OOM (where M in the formula _{represents H, NH 4} or an alkali metal) can be mentioned.

In the general formula (6e), it said n5 is preferably 5 or less integer in terms of water-soluble, the Y ³ are in that excellent sedimentation stability of the proper water solubility and composition are obtained - It is preferably COOM, and the above M is preferably H or NH ₄ .

Examples of the monomer represented by the general formula (6e) include CF ₂ = CFOCF ₂ CF ₂ CF ₂ COM (where M in the formula _{represents H, NH 4} or an alkali metal).

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

The monomer represented by the above general formula (7) is the following general formula (7a) :.
CF ₂ = CF- (CF ₂ ) _n1- Y ³ (7a)
(. Wherein, n1 represents an integer of 1 to 10, ^{Y 3} is as previously defined) monomer represented by, and the following general formula (7b):
CF ₂ = CF- (CF ₂ C (CF ₃ ) F) _n2- Y ³ (7b)
(Wherein, n2 represents an integer of 1 to 5, Y ³ is defined as the same.) At least one selected from the group consisting of a monomer represented are preferred.
The ^{Y 3} are, -SO ₃ M or -COOM is preferably, M, H, a metal atom, ^NR _{7 4,} which may imidazolium substituted, pyridinium which may have a substituent or It is preferably phosphonium which may have a substituent. The above R ⁷ represents H or an organic group.

In the above formula (7a), the above n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less. The Y ³ are points obtained stability proper water solubility and an aqueous dispersion is preferably -COOM, M is little tendency toward remaining as an impurity, that the heat resistance of the resulting molded article is improved Therefore, it is preferably H or NH _4.
Examples of the perfluorovinyl alkyl compound represented by the above formula (7a) include CF ₂ = CFCF ₂ COM (where M is the same as the above definition in the formula).

In the above formula (7b), said n2 is in terms of stability of the resulting aqueous dispersion is preferably 3 or less an integer, Y ³ is the stability of the proper water solubility and an aqueous dispersion obtained In that respect, it is preferably −COOM, and M is preferably H or NH ₄ in that it does not easily remain as an impurity and the heat resistance of the obtained molded product is improved.

The modified monomer preferably contains the modified monomer (A), and has a general formula (5a), a general formula (5c), a general formula (6a), a general formula (6b), a general formula (6c), and a general formula. It is preferable to include at least one selected from the group consisting of the compounds represented by (6d), and more preferably to contain the compound represented by the general formula (5a) or the general formula (5c).

When the modified monomer contains the modified monomer (A), the content of the polymerization unit based on the modified monomer (A) is in the range of 0.00001 to 1.0% by mass with respect to the total polymerization units of PTFE. Is preferable. As the lower limit, 0.0001% by mass is more preferable, 0.001% by mass is further preferable, and 0.005% by mass is particularly preferable. The upper limit is 0.90% by mass, 0.50% by mass, 0.40% by mass, 0.30% by mass, 0.20% by mass, 0.15% by mass, 0.10% by mass, and 0 in the order of preference. .08% by mass, 0.05% by mass, 0.01% by mass.

The content of the modified monomer in the modified PTFE may usually be in the range of 0.001 to 2.0 mol%. The lower limit of the modified monomer content is more preferably 0.01 mol%, still more preferably 0.05 mol%. The upper limit of the modified monomer content is more preferably 1.0 mol%, still more preferably 0.5 mol%, and particularly preferably 0.3 mol%.

In the production of the above-mentioned PTFE, known chain transfer agents can be used, and for example, saturated hydrocarbons such as methane, ethane, propane and butane, halogenated hydrocarbons such as chloromethane, dichloromethane and difluoroethane, and methanol. , Ethane, alcohols such as isopropanol, hydrogen and the like, but those in a gaseous state at normal temperature and pressure are preferable.

The amount of the chain transfer agent used is usually 1 to 10000 mass ppm, preferably 1 to 5000 mass ppm, based on the total amount of TFE supplied.

Further, in the production of the above-mentioned PTFE, as a dispersion stabilizer of the reaction system, 100 parts by mass of a saturated hydrocarbon having 12 or more carbon atoms which is substantially inert to the reaction and becomes liquid under the above-mentioned reaction conditions is used. It can also be used in an amount of 2 to 10 parts by mass. Further, ammonium carbonate, ammonium phosphate or the like may be added as a buffer for adjusting the pH during the reaction.

When the polymerization of PTFE is completed, an aqueous dispersion having a solid content concentration of 1.0 to 70% by mass and an average primary particle size of 50 to 500 nm can be obtained. The aqueous dispersion contains the polymer (A) and PTFE. Further, by using the polymer (A), an aqueous dispersion having particles made of PTFE having an average primary particle size of 0.5 μm or less can be obtained.
The lower limit of the solid content concentration is preferably 5% by mass, more preferably 8% by mass. The upper limit is not particularly limited, but may be 40% by mass or 35% by mass.
The lower limit of the average primary particle size is preferably 100 nm, more preferably 150 nm. The upper limit is preferably 400 nm, more preferably 350 nm.
The average primary particle size can be measured by a dynamic light scattering method. The above average primary particle size was adjusted to a solid content concentration of about 1.0% by mass to prepare an aqueous dispersion, and using a dynamic light scattering method, the temperature was 25 ° C., and the refractive index of the solvent (water) was 1.3328. , The viscosity of the solvent (water) is 0.8878 mPa · s, and can be measured 70 times in total. As the dynamic light scattering method, for example, ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) can be used.

The aqueous dispersion of PTFE obtained by the above polymerization is also stabilized and further concentrated by adding a nonionic surfactant, and various compositions are added with an organic or inorganic filler depending on the purpose. It is also preferable to use it for various purposes. The above composition has a non-adhesive and low coefficient of friction by coating on a base material made of metal or ceramics, and has excellent gloss, smoothness, abrasion resistance, weather resistance and heat resistance. It is suitable for painting rolls and cooking utensils, impregnating glass cloth, and the like.

A PTFE organosol can also be prepared from the above aqueous dispersion. The organosol can contain the PTFE and the organic solvent, and the organic solvent includes an ether solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ester solvent, an aliphatic hydrocarbon solvent, and an aromatic solvent. Examples thereof include a hydrocarbon solvent and a halogenated hydrocarbon solvent, and N-methyl-2-pyrrolidone, dimethylacetamide and the like can be preferably used. The preparation of the organosol can be carried out, for example, by the method described in International Publication No. 2012/002038.

Fine powder can be produced by coagulating the aqueous dispersion. The above-mentioned aqueous dispersion of PTFE can be used as a fine powder for various purposes after being coagulated, washed and dried. When coagulation is performed on the aqueous dispersion of PTFE, the aqueous dispersion obtained by polymerization of polymer latex or the like is usually adjusted to a polymer concentration of 5 to 20% by mass (10 to 20% by mass) using water. In some cases, the pH is adjusted to neutral or alkaline, and then the mixture is stirred vigorously in a container equipped with a stirrer rather than during the reaction. The coagulation may be carried out while adding a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, or an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid as a coagulant. The coagulation may also be continuously performed using an in-line mixer or the like.

The unaggregated PTFE concentration in the wastewater generated by the aggregation is preferably low from the viewpoint of productivity, more preferably less than 0.4% by mass, and particularly preferably less than 0.3% by mass.

By adding pigments for coloring and various fillers for improving mechanical properties before and during the above-mentioned coagulation, the pigments and fillers are uniformly mixed with the pigmented or fillerd PTFE. Fine powder can be obtained.

Drying of the wet powder obtained by coagulating the aqueous dispersion of PTFE is usually carried out by means of vacuum, high frequency, hot air or the like while keeping the wet powder in a state where it does not flow much, preferably in a stationary state. Do using. Friction between powders, especially at high temperatures, generally has an unfavorable effect on fine powder type PTFE. This is because particles made of this type of PTFE are easily fibrillated even by a small shearing force and have the property of losing the state of the original stable particle structure.

The drying is carried out at a drying temperature of 10 to 300 ° C., preferably 100 to 300 ° C. (more preferably 100 to 250 ° C.). The drying temperature may be 200 ° C. or lower.

The obtained PTFE fine powder is preferable for molding, and suitable applications include hydraulic systems such as aircraft and automobiles, fuel system tubes and the like, flexible hoses such as chemicals and steam, and electric wire coating applications. ..

It is also preferable to use the above-mentioned aqueous dispersion of PTFE or the above-mentioned PTFE fine powder as a processing aid. When used as a processing aid, by mixing the above aqueous dispersion or the above fine powder with a host polymer or the like, the melt strength during melt processing of the host polymer can be improved, and the mechanical strength, electrical properties, and difficulties of the obtained polymer can be improved. It is possible to improve flammability, drip prevention during combustion, and slidability.

It is also preferable to use the above-mentioned aqueous dispersion of PTFE or the above-mentioned PTFE fine powder as a binder for batteries and dustproof applications.

It is also preferable that the above-mentioned aqueous dispersion of PTFE or the above-mentioned PTFE fine powder is used as a processing aid after being combined with a resin other than PTFE. The aqueous dispersion or the fine powder is, for example, a raw material for PTFE described in JP-A-11-49912, US Pat. No. 5,804,654, JP-A-11-29679, and JP-A-2003-2980. Is suitable as. The processing aid using the aqueous dispersion or the fine powder is not inferior to the processing aids described in the above publications.

It is also preferable that the aqueous dispersion of PTFE is mixed with an aqueous dispersion of a melt-processable fluororesin and coagulated to obtain a co-coagulation powder. The co-coagulation powder is suitable as a processing aid.

Examples of the melt-processable fluororesin include FEP, PFA, TFE / perfluoroallyl ether copolymer, ETFE, ethylene / TFE / HFP copolymer [EFEP], and FEP is preferable.

The aqueous dispersion preferably contains the melt-processable fluororesin. Examples of the melt-processable fluororesin include FEP, PFA, TFE / perfluoroallyl ether copolymer, ETFE, EFEP and the like. The aqueous dispersion containing the melt-processable fluororesin can be used as a paint. Since the melt-processable fluororesin can sufficiently fuse the particles of the TFE polymer to each other, the film-forming property can be improved and the obtained film can be glossy.

The fluorine-free resin to which the co-coagulation powder is added may be in the form of a powder, in the form of pellets, or in the form of an emulsion. The above addition is preferably carried out while applying a shearing force by a known method such as extrusion kneading or roll kneading, in that each resin is sufficiently mixed.

It is also preferable to use the above-mentioned aqueous dispersion of PTFE as a dust control treatment agent. The dust control treatment agent is a method of mixing a dust-generating substance and subjecting the mixture to a compression-shearing action at a temperature of 20 to 200 ° C. to fibrillate the TFE polymer and suppress the dust of the dust-generating substance. , For example, it can be used in the methods of Japanese Patent No. 2827152, Japanese Patent No. 2538783, and the like.
The aqueous dispersion of PTFE can be suitably used for, for example, the dust control agent composition described in International Publication No. 2007/004250, and also in the dust control treatment method described in International Publication No. 2007/000812. It can be suitably used.

The dust control treatment agent is suitably used for dust control treatment in the fields of building materials, soil stabilizers, solidifying materials, fertilizers, incinerator ash and landfill disposal of harmful substances, explosion proofing, cosmetics and the like.

The aqueous dispersion of PTFE is also preferably used as a raw material for obtaining PTFE fibers by a dispersion spinning method. In the dispersion spinning method, the aqueous dispersion of PTFE and the aqueous dispersion of a matrix polymer are mixed, the mixture is extruded to form an intermediate fiber structure, and the intermediate fiber structure is fired. This is a method for obtaining PTFE fibers by decomposing the matrix polymer and sintering PTFE particles.

The polymer (A) can also be used to produce low molecular weight PTFE.
The low molecular weight PTFE may be produced by polymerization, or the high molecular weight PTFE obtained by polymerization may be produced by reducing the molecular weight by a known method (pyrolysis, irradiation decomposition, etc.).

Low molecular weight PTFE (also called PTFE micropowder) with a molecular weight of 600,000 or less has excellent chemical stability, extremely low surface energy, and is less likely to cause fibrillation, thus improving slipperiness and the texture of the coating film surface. It is suitable for manufacturing plastics, inks, cosmetics, paints, greases, office automation equipment members, toners and the like as additives for the purpose of making them (see, for example, Japanese Patent Laid-Open No. 10-147617).

Further, in the presence of a chain transfer agent, the polymerization initiator and the polymer (A) are dispersed in an aqueous medium, and TFE or a monomer copolymerizable with TFE is polymerized with TFE to form low molecular weight PTFE. May be obtained.

When the low molecular weight PTFE obtained by the above polymerization is used as a powder, it can be made into powder particles by coagulating the above aqueous dispersion.

In the present disclosure, the high molecular weight PTFE means a PTFE having non-melt processability and fibrillation property. On the other hand, the low molecular weight PTFE means PTFE having melt processability and not fibrillation property.

The non-melt processability means a property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D 1238 and D 2116.

The presence or absence of fibrillation can be determined by "paste extrusion", which is a typical method for molding "high molecular weight PTFE powder" which is a powder made from a polymer of TFE. Usually, paste extrusion is possible because high molecular weight PTFE has fibrillation properties. If the unbaked molded product obtained by paste extrusion does not have substantial strength or elongation, for example, if the elongation is 0% and it breaks when pulled, it can be considered that there is no fibrillation property.

The high molecular weight PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.280. The standard specific gravity is measured by a water substitution method according to ASTM D 792 using a sample molded according to ASTM D 4895-89. In the present disclosure, "high molecular weight" means that the standard specific gravity is within the above range.

The low molecular weight PTFE has a melt viscosity at 380 ° C. of 1 × 10 ^{2 to} 7 × 10 ⁵ Pa · s. In the present disclosure, "low molecular weight" means that the melt viscosity is within the above range.

The high molecular weight PTFE has an extremely high melt viscosity than the low molecular weight PTFE, and it is difficult to accurately measure the melt viscosity. On the other hand, although the melt viscosity of the low molecular weight PTFE can be measured, it is difficult to obtain a molded product that can be used for measuring the standard specific gravity from the low molecular weight PTFE, and it is difficult to measure the accurate standard specific gravity. Is. Therefore, in the present disclosure, the standard specific gravity is adopted as an index of the molecular weight of the high molecular weight PTFE, and the melt viscosity is adopted as an index of the molecular weight of the low molecular weight PTFE. For both the high molecular weight PTFE and the low molecular weight PTFE, a measuring method capable of directly specifying the molecular weight is not known.

The high molecular weight PTFE preferably has a peak temperature of 333 to 347 ° C, more preferably 335 to 345 ° C. The low molecular weight PTFE preferably has a peak temperature of 322 to 333 ° C, more preferably 324 to 332 ° C. The peak temperature corresponds to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC] for PTFE having no history of heating to a temperature of 300 ° C. or higher. Is. The peak temperature is the difference obtained by raising the temperature of PTFE, which has no history of heating to a temperature of 300 ° C or higher, under the condition of 10 ° C / min using a TG / DTA (differential thermal weight simultaneous measurement device). It can be specified as the temperature corresponding to the maximum value appearing in the heat (DTA) curve.

The high molecular weight PTFE is 333 to 347 ° C. in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC] for a PTFE having no history of heating to a temperature of 300 ° C. or higher. It is preferable that at least one or more peaks appear in the range of 1 and the amount of heat of fusion calculated from the above heat of fusion curve at 290 to 350 ° C. is 62 mJ / mg or more.

An unfired tape (raw tape) can also be obtained from the PTFE fine powder obtained by using the polymer (A).

The polymer (A), by-products produced from the polymer (A), residual monomers, etc. are recovered from the wastewater generated by the coagulation or washing and / or the off-gas generated in the drying step. Then, by purifying, the polymer (A), by-products produced from the polymer (A), residual monomers, and the like may be reused. The method for recovering and purifying is not particularly limited, but a known method can be used. For example, it can be carried out by the method described in Japanese Patent Publication No. 2011-520020.

(II) Melt Processable Fluororesin (1) In the production method of the present disclosure, the polymerization of FEP is preferably carried out at a polymerization temperature of 10 to 150 ° C. and a polymerization pressure of 0.3 to 6.0 MPaG.

The preferred monomer composition (% by mass) of FEP is TFE: HFP = (60 to 95) :( 5 to 40), more preferably (85 to 92) :( 8 to 15). The FEP may be further modified by using perfluoro (alkyl vinyl ether) as the third component within a range of 0.1 to 2% by mass of the total monomer.

In the polymerization of the FEP, the polymer (A) can be used within the range of use in the production method of the present disclosure, but usually, an amount of 0.0001 to 10% by mass is added to the aqueous medium.

In the polymerization of FEP, cyclohexane, methanol, ethanol, propanol, ethane, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, methylene chloride, methyl chloride and the like are preferably used as the chain transfer agent, preferably pH. As the buffer, it is preferable to use ammonium carbonate, disodium hydrogen phosphate or the like.

The aqueous dispersion of FEP obtained by the production method of the present disclosure may be subjected to post-treatment such as concentration if necessary, dried, powdered, and then melt-extruded to be pelletized. The aqueous medium in the aqueous dispersion of FEP may contain an additive such as a nonionic surfactant, if necessary, but may contain a water-soluble organic solvent such as a water-soluble alcohol. It may be the one which does not contain a water-soluble organic solvent.

Further, the melt extrusion can be performed by appropriately setting the extrusion conditions as long as the extrusion conditions can be generally pelletized.

In the production method of the present disclosure, the obtained FEP may have a terminal group such as _{-CF 3} , -CF ₂ H, etc. at at least one of the polymer main chain and the polymer side chain. Is the content of thermally unstable groups (hereinafter referred to as "unstable terminal groups") such as -COOH, -CH ₂ OH, -COF, -CF = CF-, -CONH ₂ , -COOCH _{3 low?} It is preferable that there is no such thing.

Since the unstable terminal group is chemically unstable, it not only lowers the heat resistance of the resin but also causes an increase in the amount of attenuation of the obtained electric wire.

In the production method of the present disclosure, the polymer at the end of polymerization can be produced so that the _{total number of unstable terminal groups and -CF 2} H terminal groups is ^{50 or less per 1 × 10 6 carbon atoms.} preferable. It is more preferably ^{less than 20 per 1 × 10 6} carbon atoms, and even more preferably 5 or less. The unstable terminal group and the -CF ₂ H terminal group may be absent and all may be a _{-CF 3 terminal group.}

Unstable end groups and -CF ₂ H end groups can _{be converted to -CF 3} end groups and stabilized by fluorination treatment. The fluorination treatment method is not particularly limited, and examples thereof include a method of exposing the polymer to a fluorinated radical source that generates fluorinated radicals under fluorinated treatment conditions. Examples of the fluorine radical source include fluorine gas, CoF ₃ , AgF ₂ , UF ₆ , OF ₂ , N ₂ F ₂ , CF ₃ OF, and halogen fluorides, for example, IF ₅ , ClF _{3, and the} like. Among them, the method of directly contacting the fluorine gas with the FEP obtained by the production method of the present disclosure is preferable, and the above contact is performed using diluted fluorine gas having a fluorine gas concentration of 10 to 50% by mass in terms of reaction control. Is preferable. The diluted fluorine gas can be obtained by diluting the fluorine gas with an inert gas such as nitrogen gas or argon gas. The fluorine gas treatment can be performed, for example, at a temperature of 100 to 250 ° C. The processing temperature is not limited to the above range, and can be appropriately set according to the situation. The fluorine gas treatment is preferably performed by continuously or intermittently supplying diluted fluorine gas into the reactor. This fluorination treatment may be carried out by a dry powder after polymerization or a pellet extruded by melting.

The FEP obtained by the manufacturing method of the present disclosure has good moldability, is less likely to cause molding defects, and has good heat resistance, chemical resistance, solvent resistance, insulation, electrical properties, and the like.

The above-mentioned method for producing a FEP powder is a method for obtaining a powder by drying and pulverizing the FEP obtained by the above-mentioned production method of the present disclosure.

The powder may be fluorinated. The above-mentioned method for producing a fluorinated powder is a method for obtaining a fluorinated powder by supplying fluorinated gas to the powder obtained by the above-mentioned method for producing a powder.

The above-mentioned method for producing pellets of FEP is a method for obtaining pellets by pelletizing the FEP obtained by the above-mentioned production method of the present disclosure.

The pellet may be fluorinated. The above-mentioned method for producing fluorinated pellets is a method for obtaining fluorinated pellets by supplying fluorinated gas to the pellets obtained by the above-mentioned method for producing fluorinated pellets.

Therefore, this FEP can be used for manufacturing various molded products such as electric wires, foamed electric wires, cables, coating materials such as wires, tubes, films, sheets, filaments and the like.

(2) In the production method of the present disclosure, the polymerization of a TFE / perfluoro (alkyl vinyl ether) copolymer such as PFA or MFA and a TFE / perfluoroallyl ether copolymer is usually carried out at a polymerization temperature of 10 to 100 ° C. The pressure is preferably 0.3 to 6.0 MPaG.

The preferred monomer composition (mol%) of the TFE / perfluoro (alkyl vinyl ether) copolymer is TFE: perfluoro (alkyl vinyl ether) = (90-99.7) :( 0.3-10), more preferably. Is (97 to 99): (1 to 3). As the perfluoro (alkyl vinyl ether), _{it is preferable to use one represented by the formula: CF 2} = CFORf ⁴ (in the formula, Rf ⁴ is a perfluoroalkyl group having 1 to 6 carbon atoms).

The preferred monomer composition (mol%) of the TFE / perfluoroallyl ether copolymer is TFE: perfluoroallyl ether = (90-99.7) :( 0.3-10), more preferably (97-). 99): (1 to 3). As the perfluoroallyl ether, _{it is preferable to use one represented by the formula: CF 2} = CFCF ₂ ORf ⁴ (in the formula, Rf ⁴ is a perfluoroalkyl group having 1 to 6 carbon atoms).

In the polymerization of the TFE / perfluoro (alkyl vinyl ether) copolymer and the TFE / perfluoroallyl ether copolymer, the polymer (A) can be used within the range of use in the production method of the present disclosure, but is usually used. , It is preferable to add in an amount of 0.0001 to 10% by mass based on the aqueous medium.

In the polymerization of the above TFE / perfluoro (alkyl vinyl ether) copolymer and TFE / perfluoroallyl ether copolymer, cyclohexane, methanol, ethanol, propanol, propane, butane, pentane, hexane, carbon tetrachloride, as chain transfer agents, Chloroform, methylene chloride, methyl chloride, methane, ethane and the like are preferably used, and ammonium carbonate, disodium hydrogen phosphate and the like are preferably used as the pH buffer.

After post-treatment such as concentration of a TFE / perfluoro (alkyl vinyl ether) copolymer such as PFA and MFA obtained by the production method of the present disclosure and an aqueous dispersion of TFE / perfluoroallyl ether copolymer as necessary. It may be pelletized by drying, powdering, and then melt-extruding. The aqueous medium in the above aqueous dispersion may contain an additive such as a nonionic surfactant, if necessary, but may contain a water-soluble organic solvent such as a water-soluble alcohol. It may be the one which does not contain a water-soluble organic solvent.

Further, the melt extrusion can be performed by appropriately setting the extrusion conditions as long as the extrusion conditions can be generally pelletized.

The above-mentioned copolymer is preferably treated with fluorine gas for the purpose of improving its heat resistance and further enhancing the effect of suppressing chemical permeation of the molded product.

Fluorine gas treatment is performed by bringing fluorine gas into contact with a chemical permeation inhibitor. However, since the reaction with fluorine is very exothermic, it is preferable to dilute the fluorine with an inert gas such as nitrogen. The amount of fluorine in the fluorine gas / inert gas mixture is 1 to 100% by mass, preferably 10 to 25% by mass. The treatment temperature is 150 to 250 ° C., preferably 200 to 250 ° C., and the fluorine gas treatment time is 3 to 16 hours, preferably 4 to 12 hours. The gas pressure of the fluorine gas treatment is in the range of 1 to 10 atm, but atmospheric pressure is preferably used. When the reactor is used at atmospheric pressure, the fluorine gas / inert gas mixture may be continuously passed through the reactor. As a result, the unstable end of the copolymer is _{converted to the -CF 3} end and becomes thermally stable.

As a molding method for the copolymer and its composition, molding methods such as compression molding, transfer molding, extrusion molding, injection molding, and blow molding can be applied as in the case of conventional PFA.

A desired molded product can be obtained by such a molding method. Examples of the molded product include a sheet, a film, a packing, a round bar, a square bar, a pipe, a tube, a round tank, a square tank, a tank, and a wafer. Carriers, wafer boxes, beakers, filter housings, flow meters, pumps, valves, cocks, connectors, nuts, wires, heat resistant wires, etc.

Of these, it is particularly suitable for tubes, pipes, tanks, connectors, etc. used for various chemical reaction devices, semiconductor manufacturing devices, and acid-based or alkaline-based chemical solution supply devices that require impermeable chemicals. Can be used.

Further, a nonionic surfactant is appropriately added to the aqueous dispersion of the TFE / perfluoro (alkyl vinyl ether) copolymer such as PFA and MFA and the TFE / perfluoroallyl ether copolymer, and if necessary, poly. A primer composition can be obtained by dissolving or dispersing ether sulfone, polyamideimide and / or polyimide, and a metal powder in an organic solvent. This primer composition is applied to a metal surface, a melt-processable fluororesin composition is applied onto the thus formed primer layer, and the melt-processable fluororesin composition layer is fired together with the primer layer to form fluorine on the metal surface. It can also be used as a resin coating method.

(3) In the production method of the present disclosure, it is preferable that ETFE is polymerized at a polymerization temperature of 10 to 100 ° C. and a polymerization pressure of 0.3 to 2.0 MPaG.

The preferred monomer composition (mol%) of ETFE is TFE: ethylene = (50-99) :( 50-1). The ETFE may be further modified by using a third monomer in a range of 0 to 20% by mass of all the monomers. Preferably, TFE: ethylene: third monomer = (63 to 94) :( 27 to 2) :( 1 to 10). Examples of the third monomer include perfluorobutylethylene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroocta-1-ene, 2,3. , 3,4,4,5,5-Heptafluoro-1-pentene (CH ₂ = CFCF ₂ CF ₂ CF ₂ H), 2-trifluoromethyl-3,3,3-trifluoropropene ((CF ₃ )) ₂ C = CH ₂ ) is preferable.

In the polymerization of ETFE, the polymer (A) can be used within the range of use in the production method of the present disclosure, but is usually added in an amount of 0.0001 to 10% by mass with respect to an aqueous medium.

In the polymerization of ETFE, it is preferable to use cyclohexane, methanol, ethanol, propanol, ethane, propane, butane, pentane, hexane, carbon tetrachloride, chloroform, methylene chloride, methyl chloride and the like as the chain transfer agent.

The aqueous dispersion of ETFE obtained by the production method of the present disclosure may be subjected to post-treatment such as concentration if necessary, dried, powdered, and then melt-extruded to be pelletized. The aqueous medium in the above aqueous dispersion may contain an additive such as a nonionic surfactant, if necessary, but may contain a water-soluble organic solvent such as a water-soluble alcohol. It may be the one which does not contain a water-soluble organic solvent.

Further, the melt extrusion can be performed by appropriately setting the extrusion conditions as long as the extrusion conditions can be generally pelletized.

The ETFE sheet can be extruded into a sheet. That is, the ETFE powder or pellet can be melted, continuously extruded from the die, and cooled to obtain a sheet-shaped molded product. Additives may be added to ETFE.

As the additive, a known additive can be appropriately used. Specific examples include ultraviolet absorbers, light stabilizers, antioxidants, infrared absorbers, flame retardants, flame retardant fillers, organic pigments, inorganic pigments, dyes and the like. Inorganic additives are preferable from the viewpoint of excellent weather resistance.
The content of the additive in the ETFE sheet is preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the total mass of the ETFE sheet.

Since the above ETFE sheet is excellent in mechanical strength and appearance, it is a membrane material (roofing material, ceiling material, outer wall material, inner wall material, covering material, etc.) for a membrane structure building (athletic facility, gardening facility, atrium, etc.). ) Is suitable.
In addition to membrane materials for membrane structures, for example, outdoor board materials (soundproof walls, windproof fences, overwave fences, garage canopies, shopping malls, pedestrian walls, roofing materials), glass shatterproof films, heat and water resistance. Sheets, building materials, etc. (tent materials for tent warehouses, membrane materials for sunshades, partial roofing materials for lighting, window materials that replace glass, membrane materials for flameproof partitions, curtains, exterior wall reinforcement, waterproof membranes, smokeproof membranes, etc. , Non-combustible transparent partition, road reinforcement, interior (lighting, wall surface, brand, etc.), exterior (tent, signboard, etc.), daily leisure goods (fishing rod, racket, golf club, projection curtain, etc.), automobile materials (roof) , Vibration damping material, body, etc.), aircraft materials, ship materials, home appliance exteriors, tanks, container inner walls, filters, construction membrane materials, electronic materials (printed boards, wiring boards, insulating films, release films, etc.), solar cells It is useful as a surface material for modules, a mirror protective material for solar thermal power generation, a surface material for solar water heaters, and the like.

(4) An electrolyte polymer precursor can also be produced using the production method of the present disclosure. In the production method of the present disclosure, the polymerization of the electrolyte polymer precursor is preferably carried out at a polymerization temperature of 10 to 100 ° C. and a polymerization pressure of 0.1 to 2.0 MPaG. The electrolyte polymer precursor is composed of a vinyl ether monomer as shown below, and can be converted into an ion-exchangeable polymer through a hydrolysis treatment.

As the vinyl ether monomer used for the electrolyte polymer precursor,
General formula (150): CF ₂ = CF-O- (CF ₂ CFY ^151- O) _n- (CFY ¹⁵² ) _m- A ¹⁵¹
(In the formula, Y ¹⁵¹ represents a fluorine atom, a chlorine atom, a -SO ₂ F group or a perfluoroalkyl group. The perfluoroalkyl group may contain _{etheric oxygen and a -SO 2 F group.} , the .n number of ^{Y 151} represents an integer of 0 to 3, which may be different or may be the same ^{.Y 152} is .m representing a fluorine atom, a chlorine atom or a -SO ₂ F group, Represents an integer of 1-5. The m Y ¹⁵² may be the same or different. A ¹⁵¹ represents -SO ₂ X ¹⁵¹ , -COZ ¹⁵¹ or -POZ ¹⁵² Z ¹⁵³ . X ¹⁵¹ represents F, Cl, Br, I, -OR ¹⁵¹ or -NR ¹⁵² R ¹⁵³ ; Z ¹⁵¹ , Z ¹⁵² and Z ¹⁵³ represent the same or different, -NR ¹⁵⁴ R ¹⁵⁵ or -OR ¹⁵⁶ . R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent the same or different alkyl, aryl, or sulfonyl-containing groups that may contain H, ammonium, alkali metal, or fluorine atoms. ) Can be mentioned. The preferred monomeric composition (mol%) of the electrolyte polymer precursor is TFE: vinyl ether = (50-99) :( 50-1), and more preferably TFE: vinyl ether = (50-93) :( 50). ~ 7).

The electrolyte polymer precursor may be modified with a third monomer within a range of 0 to 20% by mass of all the monomers. Examples of the third monomer include polyfunctional monomers such as CTFE, vinylidene fluoride, perfluoroalkyl vinyl ether, and divinylbenzene.

The electrolyte polymer precursor thus obtained is formed into, for example, a film, hydrolyzed with an alkaline solution, and treated with a mineral acid to form a polymer electrolyte film such as a fuel cell, an electrolyzer, and a redox flow battery. Can be used for.
Further, the electrolyte polymer dispersion can be obtained by hydrolyzing with an alkaline solution while maintaining the dispersed state of the electrolyte polymer precursor.
Subsequently, by heating to 120 ° C. or higher in the pressurized container, it can be dissolved in, for example, a water / alcohol mixed solvent to be in a solution state.
The solution thus obtained can be used, for example, as a binder for electrodes, or can be combined with various additives to form a cast film, and can be used, for example, for an antifouling coating film, an organic actuator, or the like.

(5) TFE / VDF Copolymer In the production method of the present disclosure, the polymerization temperature of the TFE / VDF copolymer is not particularly limited and may be 0 to 100 ° C. The polymerization pressure is appropriately determined depending on other polymerization conditions such as the polymerization temperature, but is usually 0 to 9.8 MPaG.

The preferred monomer composition (mol%) of the TFE / VDF copolymer is TFE: VDF = (40-90) :( 60-10). The TFE / VDF copolymer may be further modified by using a third monomer in the range of 0 to 50 mol% of the total monomer. Preferably, TFE: ethylene: third monomer = (40 to 85) :( 10 to 59.9) :( 0.1 to 10).

As the third monomer,
Formula: CX ¹¹ X ¹² = CX ¹³ (CX ¹⁴ X ¹⁵ ) _n11 X ¹⁶
(In the formula, X ^{11 to} X ¹⁶ represent H, F or Cl, which are the same or different, and n 11 represents an integer of 0 to 8. However, TFE and VDF are excluded.)
Formula: CX ²¹ X ²² = CX ^23- O (CX ²⁴ X ²⁵ ) _n21 X ²⁶
(In the formula, X ^{21 to} X ²⁶ represent H, F or Cl in the same or different manner, and n21 represents an integer of 0 to 8).

Further, the third monomer may be a fluorine-free ethylenic monomer. The fluorine-free ethylenic monomer is preferably selected from ethylenic monomers having 6 or less carbon atoms in terms of maintaining heat resistance and chemical resistance. For example, ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, alkyl vinyl ether (methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc.), maleic acid, itaconic acid, 3-butene acid, vinyl 4-penteneate. Examples thereof include sulfonic acid, acrylic acid and methacrylic acid.

In the polymerization of the TFE / VDF copolymer, the polymer (A) can be used within the range of use in the production method of the present disclosure, but is usually in an amount of 0.0001 to 5% by mass with respect to an aqueous medium. Added.

The TFE / VDF copolymer obtained by the polymerization may be amidated by contacting it with aqueous ammonia, ammonia gas or a nitrogen compound capable of producing ammonia.

The TFE / VDF copolymer obtained by the above-mentioned method is also preferably used as a raw material for obtaining the TFE / VDF copolymer fiber by the spinning and drawing method. The above-mentioned spinning and drawing method is a method in which a TFE / VDF copolymer is melt-spun and then cooled and solidified to obtain an undrawn yarn, and then the undrawn yarn is run in a heated tubular body to be drawn. / A method for obtaining VDF copolymer fibers.

The TFE / VDF copolymer can also be dissolved in an organic solvent to obtain a solution of the TFE / VDF copolymer. Examples of the organic solvent include nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and dimethylformamide; ketone solvents such as acetone, methylethylketone, cyclohexanone, and methylisobutylketone; ethyl acetate. , Ester solvent such as butyl acetate; Ether solvent such as tetrahydrofuran and dioxane; Further, general-purpose organic solvent having a low boiling point such as a mixed solvent thereof can be mentioned. The above solution can be used as a binder for batteries.

It is also preferable to coat the aqueous dispersion of the TFE / VDF copolymer on a porous substrate made of a polyolefin resin and use it as a composite porous membrane. It is also preferable to disperse inorganic particles or organic particles in an aqueous dispersion and coat the porous substrate for use as a composite porous membrane. The composite porous membrane thus obtained can be used as a separator for a lithium secondary battery or the like.

The melt-processable fluororesin powder can be suitably used as a powder coating material. When the powder coating material made of the melt-processable fluororesin powder is applied to the base material, a film having a smooth surface can be obtained. The melt-processable fluororesin powder having an average particle size of 1 μm or more and less than 100 μm is particularly suitable as a powder coating material used for electrostatic coating, and the melt-processable fluororesin powder having an average particle size of 100 μm or more and 1000 μm or less is particularly suitable. In particular, it is suitable as a powder coating material used for rotary coating or rotary molding.

The melt-processable fluororesin powder can be produced by a method of obtaining a powder by drying and pulverizing the melt-processable fluororesin obtained by the above-mentioned production method of the present disclosure. The production method for producing the melt-processable fluororesin powder is also one of the production methods of the present disclosure.

(III) Fluororubber In the production method of the present disclosure, in the polymerization of the fluororubber, pure water and the polymer (A) are charged in a pressure-resistant reaction vessel equipped with a stirrer, deoxidized, and a monomer is charged, and a predetermined value is obtained. Bring to temperature, add the polymerization initiator and initiate the reaction. As the pressure decreases as the reaction progresses, additional monomers are added continuously or intermittently to maintain the initial pressure. When a predetermined amount of the monomer is supplied, the supply is stopped, the monomer in the reaction vessel is purged, the temperature is returned to room temperature, and the reaction is terminated. In this case, the polymer latex can be continuously removed from the reaction vessel.

In particular, when a thermoplastic elastomer is produced as the fluororubber, as disclosed in International Publication No. 00/01741, TFE polymer particles are once synthesized at a high concentration, then diluted and further polymerized. By doing so, it is also possible to use a method capable of increasing the final polymerization rate as compared with normal polymerization.

In the polymerization of the fluororubber, appropriate conditions are selected from the viewpoint of controlling the physical properties of the target polymer and the polymerization rate, but the polymerization temperature is usually -20 to 200 ° C., preferably 5 to 150 ° C., and the polymerization pressure is usually 0. It is carried out at 5 to 10 MPaG, preferably 1 to 7 MPaG. Further, it is preferable that the pH in the polymerization medium is usually maintained at 2.5 to 13 by a known method or the like, using a pH adjuster or the like described later.

Examples of the monomer used for the polymerization of the fluororubber include TFE and a fluoroethylene unsaturated monomer other than TFE. Examples of the fluorine-containing ethylenically unsaturated monomer other than TFE include vinylidene fluoride, trifluoropropene, pentafluoropropene, hexafluorobutene, and octafluorobutene. Among them, hexafluoropropene is particularly suitable because of the properties of the elastomer obtained when it blocks the crystal growth of the polymer. Examples of the fluorine-containing ethylenically unsaturated monomer other than TFE include trifluoroethylene, CTFE, and the like, and one or more types of chlorine and / or bromine-containing monomer having a chlorine and / or bromine substituent should be used. You can also. Perfluoro (alkyl vinyl ether), for example perfluoro (methyl vinyl ether), can also be used.

In the polymerization of the fluororubber, the polymer (A) can be used within the range of use in the production method of the present disclosure, but is usually added in an amount of 0.0001 to 20% by mass with respect to the aqueous medium. It is preferably 10% by mass or less, and more preferably 2% by mass or less.

In the polymerization of the fluororubber, a known inorganic radical polymerization initiator can be used as the polymerization initiator. As the inorganic radical polymerization initiator, conventionally known water-soluble inorganic peroxides such as sodium, potassium and ammonium persulfates, perphosphates, perboronates, percarbonates or permanganates are particularly preferable. It is useful. The radical polymerization initiator further comprises a reducing agent, for example, sodium, potassium or ammonium sulphate, bisulfate, metabisulfate, hyposulfate, thiosulfate, sulphate or hyposulfate. It can be further activated by, or by a metal compound that is easily oxidized, such as ferrous, ferrous or silver salts. A suitable inorganic radical polymerization initiator is ammonium persulfate, and it is more preferable to use it in a redox system.

The concentration of the polymerization initiator added is appropriately determined by the molecular weight of the target TFE polymer and the polymerization reaction rate, but is 0.0001 to 10% by mass, preferably 0.01 with respect to 100% by mass of the total amount of the monomers. Set to an amount of ~ 5% by mass.

In the polymerization of the fluororubber, known ones can be used as the chain transfer agent, but hydrocarbons, esters, ethers, alcohols, ketones, chlorine compounds, carbonates and the like can be used, and the thermoplastic elastomer can be used. , Hydrocarbons, esters, ethers, alcohols, chlorine compounds, iodine compounds and the like can be used. Of these, acetone and isopropyl alcohol are preferable, and in the polymerization of the thermoplastic elastomer, isopentan, diethyl malonate and ethyl acetate are preferable from the viewpoint that the reaction rate does not easily decrease, and I (CF ₂ ) ₄ I, I (CF _2). ) ₆ I, ICH ₂ I and other diiodine compounds are preferable from the viewpoint that the polymer terminal can be iodinated and can be used as a reactive polymer.

The amount of the chain transfer agent used is usually 0.5 × 10 ^{-3 to} 5 × 10 ^-3 mol%, preferably 1.0 × 10 ^{-3 to} 3.5 × 10 with respect to the total amount of the supplied monomers. It is preferably ^{-3 mol%.}

Paraffin wax or the like can be preferably used as a stabilizer in the polymerization of the fluororubber, and phosphate, sodium hydroxide, potassium hydroxide or the like can be preferably used as the pH adjuster in the polymerization of the thermoplastic elastomer. ..

The fluororubber obtained by the production method of the present disclosure has a solid content concentration of 1.0 to 40% by mass and an average particle size of 0.03 to 1 μm, preferably 0.05 to 0.5 μm at the time when the polymerization is completed. , The number average molecular weight is 1,000 to 2,000,000.

The fluororubber obtained by the production method of the present disclosure can be made into a dispersion suitable for rubber molding by adding, concentrating, etc., a dispersion stabilizer such as a hydrocarbon-based surfactant, if necessary. can. The dispersion is processed by adjusting the pH, coagulating, heating and the like. Each process is performed as follows.

The pH adjustment comprises adding a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid, and / or a carboxylic acid having 5 or less carbon atoms and pK = 4.2 or less to adjust the pH to 2 or less.

The solidification is carried out by adding an alkaline earth metal salt. Examples of the alkaline earth metal salt include nitrates, chlorates and acetates of calcium or magnesium.

The pH adjustment and the coagulation may be performed first, but it is preferable to perform the pH adjustment first.

After each operation, washing is performed with the same volume of water as the fluororubber to remove a small amount of impurities such as buffer solution and salt existing in the fluororubber, and drying is performed. Drying is usually carried out in a drying oven at a high temperature of about 70 to 200 ° C. while circulating air.

The fluororubber may be a partially fluororubber or a perfluororubber.

Examples of the partially fluorinated rubber include tetrafluoroethylene (TFE) / propylene (Pr) -based fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) -based fluororubber, and the like. Of these, tetrafluoroethylene / propylene fluororubber is preferable.

The tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a fluoromonomer that provides a cross-linking site. ..

The fluororubber may be a perfluoro rubber. Examples of the perfluoro rubber include perfluoro rubber containing TFE, for example, a fluoromonomer copolymer represented by TFE / general formula (160), (130) or (140), and TFE / general formula (160), (130). ) Or (140), at least one selected from the group consisting of a fluoromonomer / a monomer copolymer giving a cross-linking site is preferable.

In the case of a TFE / PMVE copolymer, the composition is preferably 45-90 / 10-55 (mol%), more preferably 55-80 / 20-45, and even more preferably 55-. It is 70/30 to 45.

In the case of a monomer copolymer giving a TFE / PMVE / cross-linking site, it is preferably 45-89.9 / 10-54.9 / 0.01-4 (mol%), more preferably 55-77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.

In the case of the fluoromonomer copolymer represented by the general formula (160), (130) or (140) having TFE / carbon number of 4 to 12, it is preferably 50 to 90/10 to 50 (mol%). , More preferably 60 to 88/12 to 40, and even more preferably 65 to 85/15 to 35.

In the case of a fluoromonomer / monomer copolymer having a TFE / cross-linking site represented by the general formula (160), (130) or (140) having 4 to 12 carbon atoms, preferably 50 to 89.9 / 10 It is ~ 49.9 / 0.01-4 (mol%), more preferably 60-87.9 / 12-39.9 / 0.1-3.5, and even more preferably 65-84. It is .8 / 15 to 34.8 / 0.2 to 3.

If it is out of the range of these compositions, the property as a rubber elastic body is lost, and the property tends to be close to that of a resin.

Examples of the perfluoro rubber include TFE / a fluoromonomer represented by the general formula (140) / a fluoromonomer copolymer giving a cross-linking site, TFE / a perfluorovinyl ether copolymer represented by the general formula (140), and TFE. / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (160) and a TFE / a fluoromonomer represented by the general formula (160) / a monomer copolymer giving a cross-linking site. Is preferable.

Examples of the perfluoro rubber include perfluoro rubbers described in International Publication No. 97/24381, Japanese Patent Publication No. 61-5724, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Can be done.

The fluororubber has a glass transition temperature of −70 ° C. or higher, more preferably −60 ° C. or higher, and even more preferably −50 ° C. or higher, from the viewpoint of excellent compression set at high temperatures. .. Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and even more preferably -3 ° C. or lower.

For the glass transition temperature, a DSC curve is obtained by raising the temperature of 10 mg of the sample at 10 ° C./min using a differential scanning calorimeter (DSC822e manufactured by Mettler Toled), and the base before and after the secondary transition of the DSC curve is obtained. It can be obtained as the temperature indicating the midpoint of the intersection of the extension line of the line and the tangent line at the turning point of the DSC curve.

The fluororubber has a Mooney viscosity ML (1 + 20) at 170 ° C. of preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, in terms of good heat resistance. Further, in terms of good processability, it is preferably 150 or less, more preferably 120 or less, and further preferably 110 or less.

The fluororubber has a Mooney viscosity ML (1 + 20) at 140 ° C. of preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, in terms of good heat resistance. Further, in terms of good processability, it is preferably 180 or less, more preferably 150 or less, and even more preferably 110 or less.

The fluororubber has a Mooney viscosity ML (1 + 10) at 100 ° C. of preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, in terms of good heat resistance. Further, in terms of good processability, it is preferably 120 or less, more preferably 100 or less, and further preferably 80 or less.

The Mooney viscosity can be measured according to JIS K6300 at 170 ° C., 140 ° C., and 100 ° C. using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

The fluororubber obtained by the production method of the present disclosure may be in any form as long as it is obtained from the above-mentioned polymerization, and may be an aqueous dispersion after polymerization, or the above-mentioned aqueous dispersion after polymerization. It can also be used as a gum or a crumb obtained by coagulation, drying or the like by a conventionally known method. The polymer (A) used in the production method of the present disclosure can improve the stability of the aqueous dispersion, and as described above, an initiator such as an organic peroxide, iodine or a bromine compound can be used during the polymerization. It is more preferably used in a polymerization method for adding a poorly water-soluble substance such as a chain transfer agent.

The gum is a small granular mass made of fluororubber, and the crumb is a result of the fluororubber being unable to maintain a small granular shape as a gum at room temperature and fusing to each other. It is in the form of an amorphous mass.

The fluororubber can be processed into a fluororubber composition by adding a curing agent, a filler and the like.

Examples of the curing agent include polyols, polyamines, organic peroxides, organic tins, bis (aminophenol) tetraamines, bis (thioaminophenols) and the like.

Since the fluororubber composition is made of the above-mentioned fluororubber, it is excellent in that it does not substantially contain an emulsifier and is easily crosslinked during molding.

A fluororubber molded product can be obtained by molding using the above-mentioned fluororubber. The molding method is not particularly limited, and examples thereof include known methods using the above-mentioned curing agent.

The fluororubber molded body is suitable as a seal, a gasket, an electric wire coating, a hose, a tube, a laminate, an accessory, etc., and is particularly suitable for a component for a semiconductor manufacturing apparatus, an automobile part, or the like.

An aqueous dispersion of a TFE polymer can be obtained by the method for producing a TFE polymer of the present disclosure.
The solid content concentration of the aqueous dispersion of the TFE polymer is not limited, but may be, for example, 1.0 to 70% by mass. The solid content concentration is preferably more than 5.0% by mass, more preferably 8.0% by mass or more, further preferably more than 8.0% by mass, still more preferably 10.0% by mass or more. Further, it may be more than 10.0% by mass, may be more than 15.0% by mass, and may be more than 20.0% by mass. Further, 60.0% by mass or less is preferable, and 50.0% by mass or less is more preferable.
In the production method of the present disclosure, the adhesion amount is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and more preferably 1.0% by mass or less with respect to the finally obtained TFE polymer. More preferably, 0.8% by mass or less is further preferable, 0.7% by mass or less is even more preferable, and 0.6% by mass or less is particularly preferable. When the above-mentioned step (II) is not carried out, the above-mentioned solid content concentration is the solid content concentration of the aqueous dispersion obtained in the above-mentioned step (I), and the above-mentioned steps (I) and (II) are carried out. If so, the solid content concentration is the solid content concentration of the aqueous dispersion obtained in the step (II).
The aqueous dispersion may be concentrated or subjected to dispersion stabilization treatment to form a dispersion, or may be subjected to coagulation or aggregation to be recovered and dried to obtain a powder or other solid substance.
The use of the TFE polymer aqueous dispersion is not particularly limited, and as the aqueous dispersion is applied as it is, it is coated on a substrate, dried, and then fired as needed. Impregnation consisting of impregnating a porous support such as, etc., drying, and then preferably firing; Examples thereof include cast film forming for obtaining a thin film, and examples of these applications include an aqueous dispersion type paint, a binder for an electrode, a water repellent for an electrode, and the like.

The above-mentioned aqueous dispersion is a powder composed of an aqueous dispersion obtained by performing the above-mentioned polymerization, a dispersion obtained by concentrating or dispersing and stabilizing the aqueous dispersion, and a powder made of a fluoropolymer. It may be any of those dispersed in an aqueous medium in the presence of an activator.

As a method for producing the aqueous dispersion, the aqueous dispersion obtained by the polymerization is subjected to (I) anion exchange resin or anion exchange resin and cation exchange in the presence of a nonionic surfactant. Purification by the step (I) of contacting with the mixed bed containing the resin and / or (II) the step (II) of concentrating the solid content concentration so as to be 30 to 70% by mass with respect to 100% by mass of the aqueous dispersion. An aqueous dispersion can be produced.
The nonionic surfactant is not particularly limited, but those described below can be used. The anion exchange resin is not particularly limited, but known ones can be used. Further, as a method of contacting with the anion exchange resin, a known method can be used.
As a method for producing the aqueous dispersion, the aqueous dispersion obtained by the above polymerization is subjected to step (I), and the aqueous dispersion obtained in step (I) is subjected to step (II) to purify the aqueous dispersion. A liquid can be produced. Further, it is also possible to carry out the step (II) without carrying out the step (I) to produce a purified aqueous dispersion. Further, the step (I) and the step (II) can be repeated or can be combined.

As the anion exchange resin, for example, ^-N as a functional group + ^X - _{(CH 3)} 3 group (. X is representing Cl or OH) strongly basic anion exchange resin having a, ^-N + X ^- (CH ₃ ) _{Known examples include a strongly basic anion exchange resin having a 3} (C ₂ H ₄ OH) group (X is the same as above). Specifically, those described in International Publication No. 99/62858, International Publication No. 03/020386, International Publication No. 2004/078836, International Publication No. 2013/0278550, International Publication No. 2014/084399, etc. Can be mentioned.

The cation exchange resin is not particularly limited, and for example, a strongly acidic cation exchange resin having a _{−SO 3} ⁻ group as a functional group, a weakly acidic cation exchange resin having a ^{−COO − group as a functional group, and the like are known.} Among them, a strongly acidic cation exchange resin is preferable, and an H ⁺ type strongly acidic cation exchange resin is more preferable from the viewpoint of removal efficiency.

The above-mentioned "mixed bed composed of a cation exchange resin and an anion exchange resin" is not particularly limited, and when both are filled in the same column or when both are filled in different columns, both are not particularly limited. This includes the case where it is dispersed in an aqueous dispersion.

A known method is adopted as the method of concentration. Specific examples thereof include those described in International Publication No. 2007/046482 and International Publication No. 2014/084399. Examples thereof include phase separation, centrifugal sedimentation, cloud point concentration, electroconcentration, electrophoresis, filtration treatment using ultrafiltration, filtration treatment using a reverse osmosis membrane (RO membrane), nanofiltration treatment and the like. The above concentration can concentrate the fluoropolymer concentration to 30 to 70% by mass depending on the application. Concentration may impair the stability of the dispersion, in which case a dispersion stabilizer may be further added.
As the dispersion stabilizer, the nonionic surfactant and various other surfactants may be added.

The nonionic surfactant is the same as the nonionic surfactant exemplified as the nucleating agent described above, and the nonionic surfactant described above can be appropriately adopted.
The cloud point of the surfactant is a measure of the solubility of the surfactant in water. The surfactant used in the aqueous dispersion has a cloud point of about 30 ° C to about 90 ° C, preferably about 35 ° C to about 85 ° C.

The total amount of the dispersion stabilizer is a concentration of 0.5 to 20% by mass with respect to the solid content of the dispersion. If it is less than 0.5% by mass, the dispersion stability may be inferior, and if it exceeds 20% by mass, there is no dispersion effect commensurate with the abundance and it is not practical. The more preferable lower limit of the dispersion stabilizer is 2% by mass, and the more preferable upper limit is 12% by mass.

The surfactant may be removed by the concentration operation.

Depending on the application, the aqueous dispersion obtained by performing the above polymerization can also be subjected to dispersion stabilization treatment without concentration to prepare an aqueous dispersion having a long pot life. Examples of the dispersion stabilizer to be used include the same as above.

The use of the aqueous dispersion is not particularly limited, and as the aqueous dispersion is applied as it is, it is coated on a substrate, dried, and then fired as needed. Impregnation by impregnating the porous support and drying, preferably by firing; impregnation by applying on a substrate such as glass and drying, then immersing in water as necessary, peeling off the substrate to form a thin film. Examples thereof include cast films formed by obtaining, and examples of these applications include aqueous dispersion type paints, tent films, conveyor belts, printed substrates (CCL), binders for electrodes, water repellents for electrodes, and the like. ..

The aqueous dispersion may be prepared by blending a compounding agent such as a known pigment, thickener, dispersant, defoaming agent, antifreezing agent, or film forming aid, or by further compounding another polymer compound. It can be used as a water-based coating film.
Further, as an additive application, it can be used as a binder that suppresses the detachment of the active material of the electrode, a binder application, a compound application such as a drip inhibitor, and the like.

Anionic surfactants can be preferably contained for the purpose of adjusting the viscosity of the aqueous dispersion or for improving the miscibility of pigments, fillers and the like. The anionic surfactant can be appropriately added as long as there is no problem in terms of economy and environment.

Examples of the anionic surfactant include non-fluorinated anionic surfactants and fluorine-containing anionic surfactants, but fluorine-free non-fluorinated anionic surfactants, that is, anionic hydrocarbon-based surfactants. Activators are preferred.

For the purpose of adjusting the viscosity, the type is not particularly limited as long as it is a known anionic surfactant, but for example, the anionic surfactant described in International Publication No. 2013/146950 and International Publication No. 2013/146947. Agents can be used. For example, those having a saturated or unsaturated aliphatic chain having 6 to 40 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 9 to 13 carbon atoms can be mentioned. The saturated or unsaturated aliphatic chain may be either a straight chain or a branched chain, and may have a cyclic structure. The hydrocarbon may be aromatic or may have an aromatic group. The hydrocarbon may have a heteroatom such as oxygen, nitrogen or sulfur.
Examples of the anionic surfactant include alkylsulfonates, alkylsulfates, alkylarylsulfates and salts thereof; aliphatic (carboxylic) acids and salts thereof; alkyl phosphates, alkylaryl phosphates or salts thereof; and the like. However, among them, alkyl sulfonates, alkyl sulfates, aliphatic carboxylic acids or salts thereof are preferable.
As the alkyl sulfate or a salt thereof, ammonium lauryl sulfate, sodium lauryl sulfate and the like are preferable.
As the aliphatic carboxylic acid or a salt thereof, succinic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric acid, hydrododecanoic acid, or salts thereof are preferable.

The amount of the anionic surfactant added depends on the type of the anionic surfactant and other compounding agents, but is preferably 10 to 5000 mass ppm with respect to the solid content mass of the fluoropolymer.
As the lower limit of the amount of the anionic surfactant added, 50% by mass or more is more preferable, and 100% by mass or more is further preferable. If the amount added is too small, the viscosity adjusting effect is poor.
The upper limit of the amount of the anionic surfactant added is more preferably 3000 mass ppm or less, further preferably 2000 mass ppm or less. If the amount added is too large, the mechanical stability and storage stability of the aqueous dispersion may be impaired.

For the purpose of adjusting the viscosity of the aqueous dispersion, for example, methyl cellulose, alumina sol, polyvinyl alcohol, carboxylated vinyl polymer and the like can be blended in addition to the anionic surfactant.
For the purpose of adjusting the pH of the aqueous dispersion, a pH adjusting agent such as aqueous ammonia can also be added.

If necessary, the aqueous dispersion may contain other water-soluble polymer compounds as long as the characteristics of the aqueous dispersion are not impaired.
The other water-soluble polymer compounds are not particularly limited, and for example, polyethylene oxide (dispersion stabilizer), polyethylene glycol (dispersion stabilizer), polyvinylpyrrolidone (dispersion stabilizer), phenol resin, urea resin, epoxy resin, and the like. Examples thereof include melamine resin, polyester resin, polyether resin, acrylic silicone resin, silicone resin, silicone polyester resin, polyurethane resin and the like. Further, preservatives such as isothiazolone-based, azole-based, pronopol, chlorotarothalonil, methylsulfonyltetrachloropyrodin, carventazim, fluoroforbet, sodium diacetate, and diiodomethyltolylsulfone may be contained.

The production method of the present disclosure further comprises a step of recovering the TFE polymer aqueous dispersion obtained by the above method, a step of aggregating the TFE polymer in the TFE polymer aqueous dispersion, and recovering the aggregated TFE polymer. It can be preferably obtained by a production method including at least one step of the steps of the above step and the step of drying the recovered TFE polymer at 10 to 300 ° C. By including such a step, a TFE polymer powder can be obtained.

A powder can be produced by aggregating the TFE polymer contained in the aqueous dispersion. The aqueous dispersion of the TFE polymer can be used as a powder for various purposes after being aggregated, washed and dried. When agglomeration is performed on the aqueous dispersion of the TFE polymer, usually, the aqueous dispersion obtained by polymerization of polymer latex or the like is diluted with water so as to have a polymer concentration of 10 to 20% by mass. In some cases, after adjusting the pH to neutral or alkaline, the stirring is performed in a container equipped with a stirrer more vigorously than the stirring during the reaction. The aggregation may be performed by adding a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, or an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid as a coagulant while stirring. The agglomeration may also be continuously performed using an in-line mixer or the like.

In the TFE polymer aqueous dispersion obtained by the production method of the present disclosure, the average primary particle size of the TFE polymer particles is preferably 100 to 500 nm, more preferably 150 to 450 nm, still more preferably 200 to 400 nm.

When the average primary particle size of the TFE polymer particles is small, the stability of the aqueous dispersion of the TFE polymer is improved. However, if it is stabilized too much, it may take time to concentrate the TFE polymer aqueous dispersion or apply stirring and shearing force to the TFE polymer aqueous dispersion to aggregate the TFE polymer particles to obtain the TFE polymer fine powder. Since it takes time and effort, production efficiency is often impaired. Further, if the average primary particle size of the TFE polymer particles is large, the stability of the aqueous dispersion of the TFE polymer is lowered, the amount of agglomerates during the polymerization is increased, which is disadvantageous in terms of productivity, and TFE is disadvantageous after the polymerization. When the aqueous polymer dispersion is concentrated, a large amount of agglomerates are generated in the concentration tank, the sedimentation stability of the concentrate is impaired and the storage stability is lowered, and the mixture is stirred with the aqueous TFE polymer dispersion. When the TFE polymer particles are aggregated by applying a shearing force to obtain the TFE polymer fine powder, a large amount of aggregates are generated before reaching the aggregation tank from the polymerization tank, and the piping is blocked, and the yield is increased. Many manufacturing problems can occur, such as a significant reduction. When the average primary particle size of the TFE polymer particles is within the above range, the stability of the aqueous dispersion of the TFE polymer is excellent to the extent that the subsequent processability and moldability are not deteriorated, and the molded product is excellent in heat resistance and the like. Etc. are easy to obtain.

In the present disclosure, the TFE polymer aqueous dispersion used for coagulation stirring (hereinafter referred to as TFE polymer dispersion for coagulation) preferably has a TFE polymer solid content concentration of 10 to 25% by mass. The solid content concentration of the TFE polymer is preferably 10 to 22% by mass, more preferably 10 to 20% by mass. In order to increase the bulk density of the TFE polymer fine powder, it is preferable that the TFE polymer solid content concentration in the aqueous dispersion of the TFE polymer for coagulation is high. When the TFE polymer solid content concentration in the TFE polymer aqueous dispersion for coagulation is high, the degree of association of the primary particles of the TFE polymer increases, and the primary particles of the TFE polymer are densely associated and aggregated to granulate. .. When the TFE polymer solid content concentration of the TFE polymer aqueous dispersion for coagulation is less than 10% by mass, the aggregation density of the primary particles of the TFE polymer tends to be sparse, and the TFE polymer fine powder having a high bulk density is produced. Hard to get. On the other hand, if the TFE polymer solid content concentration in the aqueous dispersion of the TFE polymer for coagulation is too high, the unaggregated TFE polymer increases and the unaggregated TFE polymer solid content concentration in the aggregated wastewater increases. .. If the concentration of unaggregated TFE polymer solids in the coagulated wastewater is high, pipe blockage and wastewater treatment are costly and troublesome. In addition, the yield of the TFE polymer fine powder decreases. The unaggregated TFE polymer solid content concentration in the coagulated wastewater is preferably low, more preferably less than 0.4% by mass, and further less than 0.3% by mass, from the viewpoint of productivity of the TFE polymer fine powder. It is preferable, and less than 0.2% by mass is particularly preferable. When the TFE polymer solid content concentration of the TFE polymer aqueous dispersion for coagulation exceeds 25% by mass, it is difficult to reduce the unaggregated TFE polymer solid content concentration of the coagulated wastewater to less than 0.4% by mass. be.
The TFE polymer solid content concentration in the TFE polymer aqueous dispersion obtained in the above step (II) is approximately 10 to 45% by mass. Therefore, when the TFE polymer solid content concentration is high, water or the like may be used. Add a diluting solvent to adjust to 10-25% by mass. When the TFE polymer solid content concentration in the TFE polymer aqueous dispersion after polymerization is 10 to 25% by mass, the TFE polymer aqueous dispersion is used as it is as the TFE polymer aqueous dispersion for coagulation. be able to.

By adding a pigment for coloring and various fillers for improving mechanical properties before and during the aggregation, a TFE polymer containing a pigment or a filler in which the pigment and the filler are uniformly mixed is added. Powder can be obtained.

Drying of the wet powder obtained by aggregating the TFE polymer is usually carried out by means of vacuum, high frequency, hot air or the like while keeping the wet powder in a state where it does not flow much, preferably in a stationary state. .. Friction between powders, especially at high temperatures, generally has an unfavorable effect on fine powder type TFE polymers. For example, when the TFE polymer is PTFE, the particles made of PTFE are easily fibrilized even by a small shearing force. The drying can be performed at a drying temperature of 10 to 300 ° C., preferably 100 to 300 ° C. (more preferably 100 to 250 ° C.).

The TFE polymer powder preferably has an average particle size (average secondary particle size) of 100 to 2000 μm. The lower limit of the average secondary particle size is more preferably 200 μm or more, and further preferably 300 μm or more. The upper limit of the average secondary particle size is preferably 1000 μm or less, more preferably 800 μm or less, and particularly preferably 700 μm or less. The average particle size is a value measured according to JIS K 6891.

The above-mentioned TFE polymer powder (particularly, PTFE powder) is preferable for molding, and suitable applications include hydraulic systems such as aircraft and automobiles, fuel system tubes and the like, flexible hoses such as chemicals and steam, and electric wires. Examples include coating applications. It can also be used as a binder for batteries and as a dustproof material.

The present disclosure also provides a composition comprising a TFE polymer containing 40 mol% or more of a tetrafluoroethylene-based polymerization unit and the polymer (A).
As the TFE polymer containing 40 mol% or more of the polymerization unit based on tetrafluoroethylene and the polymer (A), the TFE weight containing 40 mol% or more of the polymerization unit based on tetrafluoroethylene described in the production method of the present disclosure. It is the same as the coalescence and the polymer (A).
The composition of the present disclosure may be a TFE polymer aqueous dispersion obtained by the above-mentioned production method of the present disclosure, or may be a powder.

In the composition of the present disclosure, the content of the polymer (A) is preferably 0.00000001% by mass or more, and more preferably 10% by mass or less, based on the TFE polymer. In the composition of the present disclosure, the lower limit of the content of the polymer (A) is more preferably 0.000000001% by mass, further preferably 0.000001% by mass, and 0.00001% by mass with respect to the above TFE polymer. Especially preferable. The upper limit is further preferably 5% by mass, further preferably 1% by mass, particularly preferably 0.5% by mass, particularly preferably 0.1% by mass, particularly preferably 0.05% by mass, and 0.01. The mass% is the most preferable.

In the composition of the present disclosure, the total amount of the TFE polymer containing 40 mol% or more of the polymerization unit based on tetrafluoroethylene and the polymer (A) is preferably 90% by mass or more, preferably 99% by mass or more. Is more preferable, and it is further preferable that the content is substantially 100% by mass.

In one embodiment of the composition of the present disclosure, it contains a fluorine-containing surfactant. By using a fluorine-containing surfactant, when the composition is an aqueous dispersion, the viscosity of the composition can be adjusted appropriately while maintaining the excellent dispersion stability of the composition, and pigments, fillers, etc. can be used. The miscibility can be improved.

It is preferred that the compositions of the present disclosure are substantially free of fluorine-containing surfactants. In the present disclosure, "substantially free of a fluorine-containing surfactant" means that the amount of the fluorine-containing surfactant is 10 mass ppm or less with respect to the fluoropolymer. The content of the fluorine-containing surfactant is preferably 1 mass ppm or less, more preferably 100 mass ppb or less, still more preferably 10 mass ppb or less, still more preferably 1 mass ppb or less. Particularly preferably, the fluorine-containing surfactant is below the detection limit as measured by liquid chromatography-mass analysis (LC / MS / MS).
The amount of the fluorine-containing surfactant can be quantified by a known method. For example, it can be quantified by LC / MS / MS analysis. First, the obtained aqueous dispersion, powder, molded body, pellets, or a fluoropolymer obtained by refining the molded body, and the fluoropolymer obtained by refining the pellets are extracted into an organic solvent of methanol, and the extract is extracted by LC / MS. / Extract the molecular weight information from the MS spectrum and confirm the agreement with the structural formula of the candidate surfactant.
Then, an aqueous solution of the confirmed surfactant having a concentration of 5 levels or more is prepared, LC / MS / MS analysis of each concentration is performed, and a calibration curve with the area area is prepared.
The obtained aqueous dispersion, powder, or powder obtained by crushing a molded product can be quantitatively measured by performing Soxhlet extraction with methanol and performing LC / MS / MS analysis on the extract.

That is, the content of the fluorine-containing surfactant can be measured, for example, by adding methanol to the composition, performing extraction, and performing LC / MS / MS analysis on the obtained extract.
In order to further improve the extraction efficiency, treatment by Soxhlet extraction, ultrasonic treatment or the like may be performed.
Molecular weight information is extracted from the obtained LC / MS / MS spectra, and agreement with the structural formula of the candidate fluorine-containing surfactant is confirmed.
After that, an aqueous solution having a content of 5 levels or more of the confirmed fluorine-containing surfactant was prepared, and LC / MS / MS analysis was performed on the aqueous solution having each content, and the content and the area area with respect to the content were determined. Plot the relationship and draw a calibration curve.
Then, using the calibration curve, the area area of the LC / MS / MS chromatogram of the fluorine-containing surfactant in the extract can be converted into the content of the fluorine-containing surfactant.

The fluorine-containing surfactant is the same as that exemplified in the above-mentioned production method of the present disclosure. For example, it may be a surfactant containing a fluorine atom having a total carbon number of 20 or less in the portion excluding the anionic group, and the molecular weight of the anionic portion is 1000 or less, more preferably 800 or less, still more preferably 600 or less. It may be a surfactant containing, and it may be a fluorine-containing surfactant having a LogPOW of 3.5 or less.
Examples of the fluorine-containing surfactant include ^{a compound represented by the above general formula (N 0} ), specifically, a compound represented by the general formula (N ¹ ) and a compound represented by the general formula (N ² ). Examples thereof include a compound represented by the general formula (N ³ ), a compound represented by the general formula (N ⁴ ), and a compound represented by the general formula (N ⁵ ). More specifically, the perfluorocarboxylic acid (I) represented by the general formula (I), the ω-H perfluorocarboxylic acid (II) represented by the general formula (II), and the general formula (III) are represented. Perfluoropolyether carboxylic acid (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by the general formula (V), Perfluoroalkyl sulfonic acid (VI) represented by the general formula (VI), ω-H perfluorosulfonic acid (VII) represented by the general formula (VII), and perfluoroalkyl represented by the general formula (VIII). The alkylene sulfonic acid (VIII), the alkylalkylene carboxylic acid (IX) represented by the general formula (IX), the fluorocarboxylic acid (X) represented by the general formula (X), and the alkoxy represented by the general formula (XI). Examples thereof include fluorosulfonic acid (XI), a compound represented by the general formula (XII) (XII), and a compound represented by the general formula (XIII) (XIII).

The composition of the present disclosure preferably has a standard specific density (SSG) of 2.280 or less. The upper limit of the standard specific density is more preferably 2.250, further preferably 2.230, still more preferably 2.200 or less, particularly preferably 2.195, and even more preferably 2.190 or less. The lower limit of the standard density is not limited, but is, for example, 2.130.
The standard specific gravity is measured by a water substitution method according to ASTM D 792 using a sample molded according to ASTM D 4895-89.

The compositions of the present disclosure can be appropriately adopted for the applications described for the various TFE polymers described above.

Although the embodiments have been described above, it will be understood that various modifications of the embodiments and details are possible without departing from the spirit and scope of the claims.

Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to such examples.

Each numerical value of the example was measured by the following method.

Average primary particle size Measured by dynamic light scattering method. A fluoropolymer aqueous dispersion adjusted to a fluoropolymer solid content concentration of about 1.0% by mass was prepared, and measured using ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) at 25 ° C. for a total of 70 times. The refractive index of the solvent (water) was 1.3328, and the viscosity of the solvent (water) was 0.8878 mPa · s.

Standard density (SSG)
Samples molded according to ASTM D 4895-89 were used and measured by the water substitution method according to ASTM D 792.

For the PTFE powder obtained in the peak temperature example, a heat of fusion curve was drawn under the condition of a heating rate of 10 ° C./min using a differential scanning calorimeter [DSC], and the maximum value of the peak appearing in the heat of fusion curve was reached. The temperature corresponding to the above was taken as the peak temperature of PTFE.

Solid content concentration of the PTFE aqueous dispersion 1 g of the PTFE aqueous dispersion was dried in a blower dryer at 150 ° C. for 60 minutes, and the ratio of the mass of the heating residue to the mass (1 g) of the aqueous dispersion was a percentage. Use the value represented by.

Molecular weight measurement of polyacrylic acid Using gel permeation chromatograph GPC (Agilent 1260 Infinity II), differential refractometer detector RI as a detector, column is TSKgei GMPW _XL 1 piece, G3000PW _XL 1 piece (φ7.8 mm × 30 cm, Tosoh Corporation), the solvent was 0.1 M Tris (0.1 M KCl, pH 9) / acetonitrile (8/2, vol / vol), the flow velocity was 0.5 ml / min, and the column temperature was 28 ° C. The sample concentration at the time of driving was 2.0 mg / ml. Polyethylene oxide (PEO) and polyethylene glycol (PEG) were used as standard samples. The preparation (number average molecular weight 2.0 × 10 ⁴ or more), the PEO molecular weight region, the molecular weight was measured by using a low molecular weight region of a preparation (number average molecular weight 2.0 × 10 below ^4), the PEG.

A PTFE aqueous dispersion diluted to an aspect ratio solid content concentration of about 1% by mass was observed with a scanning electron microscope (SEM), and image processing was performed on 200 or more randomly selected particles to obtain the major axis. It was calculated from the average of the minor axis ratios.

Thermal instability index (TII)
Measured according to ASTM D 4895-89.

Approximately 10 mg of powder with no history of heating to a temperature of 0.1% mass reduction temperature of 300 ° C or higher is precisely weighed, stored in a dedicated aluminum pan, and measured using a TG / DTA (differential thermal weight simultaneous measurement device). do. The 0.1% mass reduction temperature is the temperature corresponding to the point where the weight of the aluminum pan is reduced by 0.1 mass% by raising the temperature of the aluminum pan under the condition of 10 ° C./min in the temperature range from 25 ° C. to 600 ° C. in the atmosphere. And.

Approximately 10 mg of powder with no history of heating to a temperature of 1.0% mass reduction temperature of 300 ° C or higher is precisely weighed, stored in a dedicated aluminum pan, and measured using a TG / DTA (differential thermal weight simultaneous measurement device). do. The 1.0% mass reduction temperature is the temperature corresponding to the point where the weight of the aluminum pan is reduced by 1.0 mass% by raising the temperature of the aluminum pan under the condition of 10 ° C./min in the temperature range from 25 ° C. to 600 ° C. in the atmospheric atmosphere. And.

HFP content The HFP content is 0. The ratio of the absorbance at ^{982 cm -1} / the absorbance at ^{935 cm -1} from the infrared absorbance measured by FT-IR of the thin film disk made by press-molding the PTFE powder. Obtained by multiplying by 3.

Example 1
In a SUS reactor with an internal volume of 6 L and a stirrer, 3600 g of deionized degassed water, 180 g of paraffin wax, 0.500 g of oxalic acid, and 1.08 g of sodium polyacrylate (number average molecular weight is 0.6). × 10 ⁴ , the weight average molecular weight was 0.9 × 10 ⁴ ) was added, the reactor was sealed, the inside of the system was replaced with nitrogen, and oxygen was removed. The temperature of the reactor was raised to 70 ° C., TFE was filled in the reactor, and the internal pressure of the reactor was 2.76 MPaG. Polymerization was immediately initiated by continuously charging a 1.0% by mass aqueous potassium permanganate solution into the reactor. TFE was charged so that the reaction pressure was constant at 2.76 MPaG. When 150 g of TFE was charged, stirring was stopped and depressurization was performed until the reactor reached atmospheric pressure. By the end of the reaction, 32.9 g of potassium permanganate aqueous solution was charged. The contents were taken out from the reactor, cooled, and then the paraffin wax was separated to obtain a PTFE aqueous dispersion.
The solid content concentration of the obtained PTFE aqueous dispersion was 4.2% by mass, and the average primary particle size was 92 nm. The 0.1% mass loss temperature was 301 ° C., and the 1.0% mass loss temperature was 450 ° C. The peak temperature determined from DSC was 329 ° C. From this, it was found that low molecular weight PTFE was obtained.

Example 2
To a reactor made of SUS with an internal volume of 3 L and a stirrer, 1763 g of deionized degassed water, 90 g of paraffin wax, and 38.6 g of the PTFE aqueous dispersion of Example 1 were added, the reactor was sealed, and the inside of the system was sealed. Was replaced with nitrogen to remove oxygen. The temperature of the reactor was raised to 85 ° C., TFE was filled in the reactor, and the internal pressure of the reactor was 2.70 MPaG. As a polymerization initiator, 0.5724 g of disuccinic acid peroxide was charged. TFE was charged so that the reaction pressure was constant at 2.70 MPaG. Immediately, an aqueous solution of disuccinic acid peroxide having a concentration of 2.0% by mass was continuously charged into the reactor. 12.0 g of sodium dodecyl sulfate, 0.05 g of iron (II) sulfate heptahydrate, and 0.02 g of sulfuric acid having a concentration of 95% were dissolved in 288 g of deionized water and stirred to obtain a uniform aqueous solution A. Obtained. Immediately after charging the initiator, this aqueous solution A was continuously charged into the reactor. When 200 g of TFE was charged, stirring was stopped and the reactor was depressurized until it reached atmospheric pressure. By the end of the reaction, 24.2 g of aqueous solution A and 37.5 g of disuccinic acid peroxide aqueous solution were charged. The contents were taken out from the reactor, cooled, and then the paraffin wax was separated to obtain a PTFE aqueous dispersion.
The solid content concentration of the obtained PTFE aqueous dispersion was 9.9% by mass, and the average primary particle size was 351 nm.
The obtained PTFE aqueous dispersion was solidified under high speed stirring conditions. The solidified wet powder was dried at 210 ° C. for 18 hours. The SSG of the obtained PTFE powder was 2.179, and the thermal instability index (TII) was 49. The 0.1% mass loss temperature was 422 ° C., and the 1.0% mass loss temperature was 492 ° C. The peak temperature determined from DSC was 338 ° C. The aspect ratio was 1.58.

Example 3
1800 g of deionized degassed water, 90 g of paraffin wax, 0.25 g of oxalic acid, and 0.54 g of sodium polyacrylate (number average molecular weight is 0.6) in a SUS reactor with an internal volume of 3 L and a stirrer. × 10 ⁴ , the weight average molecular weight was 0.9 × 10 ⁴ ) was added, the reactor was sealed, the inside of the system was replaced with nitrogen, and oxygen was removed. The temperature of the reactor was raised to 70 ° C., 6.6 g of HFP was charged, and the reactor was further filled with TFE to bring the internal pressure of the reactor to 2.70 MPaG. Polymerization was immediately initiated by continuously charging a 1.0% by mass aqueous potassium permanganate solution into the reactor. TFE was charged so that the reaction pressure was constant at 2.70 MPaG. When 45 g of TFE was charged, stirring was stopped and depressurization was performed until the reactor reached atmospheric pressure. By the end of the reaction, 16.5 g of potassium permanganate aqueous solution was charged. The contents were taken out from the reactor, cooled, and then the paraffin wax was separated to obtain a PTFE aqueous dispersion.

The solid content concentration of the obtained PTFE aqueous dispersion was 2.4% by mass, and the average primary particle size was 46 nm. The 0.1% mass loss temperature was 298 ° C., and the 1.0% mass loss temperature was 377 ° C. The peak temperature was 326 ° C. The amount of HFP modification was 0.12% by mass. From this, it was found that low molecular weight PTFE was obtained.

Example 4
Internal volume 3L equipped with a stirrer made of SUS reactor, deionized deaerated water of 1760 g, 90 g of paraffin wax, and polyacrylic acid (number average molecular weight of 0.273g is 0.7 × 10 ^4, weight average molecular weight 1.2 × 10 ⁴ ) was added, and a small amount of aqueous ammonia was added so that the pH became 10.1. The reactor was sealed and the system was replaced with nitrogen to remove oxygen. The temperature of the reactor was raised to 70 ° C., an aqueous solution prepared by dissolving 1.8 g of HFP and 0.25 g of ammonium oxalate in 40 g of deionized water was charged, and the reactor was further filled with TFE to fill the reactor. The internal pressure of was set to 2.70 MPaG. Polymerization was immediately started by continuously charging the reactor with an aqueous solution of potassium permanganate having a concentration of 0.5% by mass. TFE was charged so that the reaction pressure was constant at 2.70 MPaG. When 60 g of TFE was charged, stirring was stopped and depressurization was performed until the reactor reached atmospheric pressure. By the end of the reaction, 39.0 g of an aqueous potassium permanganate solution was charged. The contents were taken out from the reactor, cooled, and then the paraffin wax was separated to obtain a PTFE aqueous dispersion.

The solid content concentration of the obtained PTFE aqueous dispersion was 3.2% by mass, and the average primary particle size was 139 nm. The 0.1% mass loss temperature was 293 ° C., and the 1.0% mass loss temperature was 404 ° C. The peak temperature was 329 ° C. The amount of HFP modification was 0.05% by mass. From this, it was found that low molecular weight PTFE was obtained.

Example 5
1760 g of deionized degassed water, 90 g of paraffin wax, and 0.546 g of ammonium polyacrylate (number average molecular weight is 0.6 × 10 ⁴ , weight average molecular weight) in a SUS reactor with an internal volume of 3 L and a stirrer. 1.0 × 10 ⁴ ) was added, the reactor was sealed, the inside of the system was replaced with nitrogen, and oxygen was removed. The temperature of the reactor was raised to 70 ° C., an aqueous solution prepared by dissolving 1.7 g of HFP and 0.25 g of ammonium oxalate in 40 g of deionized water was charged, and the reactor was further filled with TFE to fill the reactor. The internal pressure of was set to 2.70 MPaG. Polymerization was immediately started by continuously charging the reactor with an aqueous solution of potassium permanganate having a concentration of 0.5% by mass. TFE was charged so that the reaction pressure was constant at 2.70 MPaG. When 90 g of TFE was charged, stirring was stopped and depressurization was performed until the reactor reached atmospheric pressure. By the end of the reaction, 40.8 g of potassium permanganate aqueous solution was charged. The contents were taken out from the reactor, cooled, and then the paraffin wax was separated to obtain a PTFE aqueous dispersion.
The solid content concentration of the obtained PTFE aqueous dispersion was 4.7% by mass, and the average primary particle size was 165 nm. The 0.1% mass loss temperature was 300 ° C., and the 1.0% mass loss temperature was 426 ° C. The peak temperature was 330 ° C. The amount of HFP modification was 0.04% by mass. From this, it was found that low molecular weight PTFE was obtained.

Example 6
1760 g of deionized degassed water, 90 g of paraffin wax, and 0.273 g of sodium polyacrylate (number average molecular weight is 0.6 × 10 ⁴ , weight average) in a SUS reactor with an internal volume of 3 L and a stirrer. The molecular weight was 0.9 × 10 ⁴ ), the reactor was sealed, the inside of the system was replaced with nitrogen, and oxygen was removed. The temperature of the reactor was raised to 70 ° C., an aqueous solution prepared by dissolving 1.8 g of HFP and 0.5 g of ammonium oxalate in 40 g of deionized water was charged, and the reactor was further filled with TFE to fill the reactor. The internal pressure of was set to 2.70 MPaG. Polymerization was immediately started by continuously charging the reactor with an aqueous solution of potassium permanganate having a concentration of 0.5% by mass. TFE was charged so that the reaction pressure was constant at 2.70 MPaG. When 64 g of TFE was charged, stirring was stopped and the reactor was depressurized to atmospheric pressure. After that, TFE was filled, the internal pressure of the reactor was set to 2.70 MPaG, and stirring was restarted. 6.9 g of lauric acid, 142 g of deionized water and 9.7 g of a 10 mass% aqueous ammonia solution were dissolved and stirred to obtain a uniform aqueous solution B. Stirring was restarted, and immediately, the aqueous solution B was continuously charged into the reactor. Stirring was stopped when 640 g of TFE was charged and depressurized until the reactor reached atmospheric pressure. By the end of the reaction, 55 g of potassium permanganate aqueous solution and 41 g of aqueous solution B were charged. The contents were taken out from the reactor, cooled, and then the paraffin wax was separated to obtain a PTFE aqueous dispersion.
The solid content concentration of the obtained PTFE aqueous dispersion was 25.2% by mass, and the average primary particle size was 237 nm. The aspect ratio of the PTFE particles in the PTFE aqueous dispersion was 1.18.
The obtained PTFE aqueous dispersion was solidified under high speed stirring conditions. The solidified wet powder was dried at 210 ° C. for 18 hours. The SSG of the obtained PTFE powder was 2.184, and the thermal instability index (TII) was 46. The amount of HFP modification was 0.01% by mass.
The 0.1% mass loss temperature was 344 ° C., and the 1.0% mass loss temperature was 489 ° C. The peak temperature was 343 ° C.

Claims (26)

A method for producing a tetrafluoroethylene polymer containing 40 mol% or more of polymerization units based on tetrafluoroethylene.
The step (I) of polymerizing tetrafluoroethylene in an aqueous medium in the presence of the polymer (A) is included.
The polymer (A) is a polymer containing a polymerization unit based on at least one selected from the group consisting of vinylphosphonic acid, vinyl sulfonic acid, and (meth) acrylic acid, and a group consisting of salts thereof. A method for producing a tetrafluoroethylene polymer, which is selected from at least one kind. The production method according to claim 1, wherein the polymer (A) is a polymer containing a polymerization unit based on (meth) acrylic acid or a salt thereof. The production method according to claim 1 or 2, wherein the polymer containing the polymerization unit based on (meth) acrylic acid has a content of the polymerization unit based on (meth) acrylic acid of 50 mol% or more. The production method according to any one of claims 1 to 3, wherein the step (I) is a production method in which the amount of the polymer (A) is 0.0001 to 10% by mass with respect to an aqueous medium. The production method according to any one of claims 1 to 4, wherein the step (I) is a step performed in the presence of a redox initiator. The production method according to any one of claims 1 to 5, wherein the step (I) is carried out substantially in the absence of a fluorine-containing surfactant. The production method according to any one of claims 1 to 6, wherein the step (I) is performed in the presence of a hydrocarbon-based surfactant. The production method according to claim 7, wherein the hydrocarbon-based surfactant is an ammonium carboxylic acid salt. The production method according to any one of claims 1 to 7, wherein in the step (I), an aqueous solution containing a hydrocarbon-based surfactant and having a pH of 5.0 or more is added. The step (I) is a step of obtaining particles containing a polymerization unit based on tetrafluoroethylene.
The production method according to any one of claims 1 to 9, further comprising a step (II) of polymerizing tetrafluoroethylene in an aqueous medium containing the particles obtained in the step (I). The production method according to claim 10, wherein the step (I) is a step of obtaining an aqueous dispersion having a particle concentration of 20% by mass or less. The production method according to claim 10 or 11, wherein the step (II) is a step performed in the presence of an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator. The production method according to any one of claims 10 to 12, wherein the step (II) is carried out substantially in the absence of a fluorine-containing surfactant. The production method according to any one of claims 1 to 13, wherein the tetrafluoroethylene polymer is a perfluoropolymer. The production method according to any one of claims 1 to 14, wherein the tetrafluoroethylene polymer is polytetrafluoroethylene. The production method according to any one of claims 1 to 15, wherein the tetrafluoroethylene polymer is modified polytetrafluoroethylene. A tetrafluoroethylene polymer containing 40 mol% or more of a polymerization unit based on tetrafluoroethylene and a polymer (A) are contained.
The polymer (A) is at least one selected from the group consisting of a polymer containing a polymerization unit based on vinyl phosphonic acid, vinyl sulfonic acid, and (meth) acrylic acid, and a salt thereof. Characteristic composition. The composition according to claim 17, wherein the polymer (A) is a polymer containing a polymerization unit based on (meth) acrylic acid or a salt thereof. The composition according to claim 17 or 18, wherein the polymer containing the (meth) acrylic acid-based polymerization unit has a content of 50 mol% or more of the (meth) acrylic acid-based polymerization unit. The composition according to any one of claims 17 to 19, wherein the content of the polymer (A) is 10% by mass or less with respect to the tetrafluoroethylene polymer. The composition according to any one of claims 17 to 20, wherein the tetrafluoroethylene polymer is a perfluoropolymer. The composition according to any one of claims 17 to 21, wherein the tetrafluoroethylene polymer is polytetrafluoroethylene. The composition according to any one of claims 17 to 22, wherein the tetrafluoroethylene polymer is modified polytetrafluoroethylene. The composition according to any one of claims 17 to 23, wherein the standard specific density is 2.280 or less. The composition according to any one of claims 17 to 24, which is substantially free of a fluorine-containing surfactant. The composition according to any one of claims 17 to 25, which is a powder.