Method for producing fluorine-containing elastomer

Abstract

Specifically disclosed is a method for producing a fluorine-containing elastomer, which is characterized by comprising a polymerization step for obtaining a fluorine-containing elastomer by emulsion-polymerizing a fluorine-containing monomer in an aqueous medium in the presence of a fluorine-containing compound (A) that contains a hydrophilic group and a functional group that can react in radical polymerization, and a hydrocarbon-based surfactant (B). The amount of the hydrocarbon surfactant (B) is equal to 3 ppm to 1000 ppm of the aqueous medium, and the emulsion polymerization is carried out in the presence of a redox initiator.

Description

[0001] This application is a divisional application. The application number of the original application is 202080050438.4, the application date is July 16, 2020, and the name of the invention is "Method and composition for manufacturing fluorinated elastomers". Technical Field

[0002] The present invention relates to a method for making fluoroelastomers and compositions. Background Art

[0003] Fluoroelastomers exhibit excellent chemical resistance, solvent resistance, and heat resistance, and are therefore used in a wide range of industrial fields such as the automotive industry, semiconductor industry, and chemical industry as raw materials for sealing materials used under harsh conditions.

[0004] These fluorinated elastomers are produced by emulsion polymerization of fluorinated monomers.

[0005] For example, Patent Document 1 describes a method for producing a fluorine-containing elastomer, which comprises adding a water-soluble free radical polymerization initiator to carry out emulsion polymerization of a fluorine-containing monomer, and is characterized in that the emulsion polymerization is carried out in the presence of a compound (1) and a fluorine-containing compound (2), wherein the compound (1) has a functional group capable of reacting in free radical polymerization and a hydrophilic group, and the fluorine-containing compound (2) has a fluorocarbon group in which 1 to 6 carbon atoms directly bonded to a fluorine atom are continuously bonded and a hydrophilic group.

[0006] Patent document 2 describes a method for producing a fluorinated elastomeric polymer, which comprises polymerizing a fluorinated monomer in an aqueous medium in the presence of a fluorinated vinyl-containing emulsifier, a vulcanization point monomer (b1) and / or a saturated aliphatic compound (b2) having a bromine atom and / or an iodine atom, and is characterized in that the fluorinated vinyl-containing emulsifier is composed of a compound having a free radical polymerizable unsaturated bond and a hydrophilic group in the molecule.

[0007] Patent document 3 describes a method for producing a fluorinated elastomeric polymer, which comprises polymerizing a fluorinated monomer in an aqueous medium in the presence of a fluorinated vinyl-containing emulsifier and a chain transfer agent, and is characterized in that the fluorinated vinyl-containing emulsifier is composed of a compound having a free radical polymerizable unsaturated bond and a hydrophilic group in the molecule.

[0008] Patent document 4 describes a method for producing a fluorinated copolymer emulsion, in which a monomer mixture containing tetrafluoroethylene and propylene is subjected to emulsion polymerization at a polymerization temperature in the range of 50°C to 100°C in the presence of an aqueous medium, an anionic emulsifier and a pyrolytic free radical polymerization initiator to produce an emulsion of a fluorinated copolymer. The method is characterized in that the aqueous medium is composed of water alone or of water and a water-soluble organic solvent, the content of the water-soluble organic solvent is less than 1 part by mass relative to 100 parts by mass of water, and the amount of the anionic emulsifier used is 1.5 parts by mass to 5.0 parts by mass relative to 100 parts by mass of the generated fluorinated copolymer.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: International Publication No. 2008 / 001895

[0012] Patent Document 2: Japanese Patent Application Publication No. 2005-320499

[0013] Patent Document 3: Japanese Patent Application Publication No. 2005-320500

[0014] Patent Document 4: International Publication No. 2012 / 111770 Summary of the invention

[0015] Problems to be solved by the invention

[0016] The present invention aims to provide a method for producing a fluorinated elastomer using a hydrocarbon-based surfactant, which method can suppress the adhesion of a polymer to a polymerization tank and produce a desired amount of fluorinated elastomer in a short time despite the use of a hydrocarbon-based surfactant.

[0017] Means for solving problems

[0018] The present invention provides a method for producing a fluorine-containing elastomer, which is characterized in that it includes the following steps: in the presence of a fluorine-containing compound (A) containing a functional group capable of reacting in free radical polymerization and a hydrophilic group and a hydrocarbon-based surfactant (B), emulsion polymerization of a fluorine-containing monomer in an aqueous medium to obtain a fluorine-containing elastomer.

[0019] The fluorine-containing compound (A) is preferably a compound having a radically polymerizable unsaturated bond-containing group as a functional group capable of reacting in radical polymerization.

[0020] It is preferred that the fluorine-containing compound (A) and the hydrocarbon-based surfactant (B) are compounds each containing an anionic and / or nonionic hydrophilic group.

[0021] The hydrophilic group of the fluorine-containing compound (A) is preferably -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2 (in each formula, M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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. ).

[0022] The fluorine-containing compound (A) is preferably a compound represented by the following formula (A).

[0023] CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (A)

[0024] (Where X i , X j and X k Each independently represents F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a connecting group; Z 1 and Z 2 Each independently represents H, F or CF3; k represents 0 or 1. i , X k , X j , R a , Z 1 and Z 2 At least one of them contains a fluorine atom. Where k is 0, R a is a connecting group other than a single bond. )

[0025] The fluorine-containing compound (A) is more preferably at least one selected from the group consisting of a monomer represented by the following general formula (5), a monomer represented by the following general formula (6), and a monomer represented by the following general formula (7).

[0026] CX2=CY(-CZ2-O-Rf-Y 3 ) (5)

[0027] (wherein, X is the same or different and is -H or -F, Y is -H, -F, alkyl or fluorinated alkyl, and Z is the same or different and is -H, -F, alkyl or fluorinated alkyl. Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. Y 3Same as above.)

[0028] CX2=CY(-O-Rf-Y 3 ) (6)

[0029] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. 3 Same as above.)

[0030] CX2=CY(-Rf-Y 3 ) (7)

[0031] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. 3 Same as above.)

[0032] The fluorine-containing compound (A) is more preferably at least one selected from the group consisting of a monomer represented by the following general formula (5b), a monomer represented by the following general formula (5c), and a monomer represented by the following general formula (5d).

[0033] CH2=CF(-CF2-O-Rf-Y 3 )(5b)

[0034] (In the formula, Rf and Y 3 Same as above.)

[0035] CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5c)

[0036] (In the formula, each X 2 The same, represents F or H. n5 represents 0 or an integer from 1 to 10, Y 3 Same as above.)

[0037] CF2=CFCF2-O-Rf-Y 3 (5d)

[0038] (In the formula, Rf and Y 3 Same as above)

[0039] The hydrocarbon-based surfactant (B) is preferably a surfactant represented by the following general formula (γ).

[0040] R 14 -Y 3 (γ)

[0041] (Where R 14 represents an aliphatic hydrocarbon group which may contain a carbonyl group. 3 It is a hydrophilic group.

[0042] Y in the above general formula (γ) 3 Preferably -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2 (in each formula, M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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.

[0043] In the above general formula (γ), R 14 Preferred is an aliphatic hydrocarbon group containing one or more carbonyl groups.

[0044] In the above general formula (γ), R 14 An aliphatic hydrocarbon group having no carbonyl group is preferred.

[0045] The hydrocarbon-based surfactant (B) is preferably a surfactant represented by the following general formula.

[0046] CH3-(CH2) n -Y 5

[0047] (where n is an integer from 1 to 2000, Y 5 is a hydrophilic group.)

[0048] Y 5 Preferably -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2 (in each formula, M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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.

[0049] The amount of the fluorine-containing compound (A) is preferably an amount corresponding to 5 ppm to 5000 ppm of the aqueous medium.

[0050] The amount of the hydrocarbon-based surfactant (B) is preferably an amount corresponding to 3 ppm to 5000 ppm of the aqueous medium.

[0051] It is preferred that the fluorine-containing compound (A) and the hydrocarbon surfactant (B) are present in an aqueous medium before all the polymerization initiators used in the polymerization step are present.

[0052] In the above polymerization step, when the solid content concentration of the fluorinated elastomer in the aqueous medium is at most 1.0 mass %, it is preferred that the hydrocarbon surfactant (B) is present in the aqueous medium.

[0053] In the above-mentioned polymerization step, it is preferred that the above-mentioned hydrocarbon-based surfactant (B) is present in the aqueous medium before the presence of the polymerization initiator.

[0054] In the above polymerization step, when the solid content concentration of the fluorinated elastomer in the aqueous medium is at most 1.0 mass %, it is preferred that the fluorinated compound (A) is present in the aqueous medium.

[0055] In the above-mentioned polymerization step, it is preferred that the above-mentioned fluorine-containing compound (A) is present in an aqueous medium before the presence of a polymerization initiator.

[0056] The emulsion polymerization is preferably carried out in the presence of a polymerization initiator, and the polymerization initiator is preferably a water-soluble polymerization initiator.

[0057] The above-mentioned fluorinated elastomer preferably contains -CH2- in the main chain.

[0058] The above-mentioned fluorinated elastomer preferably contains vinylidene fluoride units.

[0059] In the above-mentioned fluorine-containing elastomer, the composition of vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene is preferably (32 to 85) / (10 to 34) / (0 to 34) (mol %).

[0060] The above-mentioned emulsion polymerization is preferably carried out in the presence of a redox initiator.

[0061] The temperature of the emulsion polymerization is preferably 10°C to 120°C.

[0062] The above-mentioned emulsion polymerization is preferably iodine transfer polymerization or bromine transfer polymerization.

[0063] The present invention also provides a composition comprising a fluorinated elastomer and a hydrocarbon surfactant (B), wherein the fluorinated elastomer comprises a structural unit derived from a fluorinated compound (A) having a functional group capable of reacting in free radical polymerization and a hydrophilic group.

[0064] The above-mentioned fluorine-containing elastomer preferably contains a -CH2I structure.

[0065] The above-mentioned fluorine-containing elastomer preferably contains a -CF2CH2I structure.

[0066] In the above fluorine-containing elastomer, the amount of -CF2CH2I structure is preferably 0.05 mol% to 1.50 mol% based on 100 mol% of -CH2- structure.

[0067] The composition of the present invention preferably contains substantially no fluorinated surfactant.

[0068] Effects of the Invention

[0069] According to the present invention, there is provided a method for producing a fluorine-containing elastomer, which is a method for producing a fluorine-containing elastomer using a hydrocarbon-based surfactant, and which can suppress the adhesion of a polymer to a polymerization tank despite the use of a hydrocarbon-based surfactant and can produce a desired amount of fluorine-containing elastomer in a short time. DETAILED DESCRIPTION

[0070] Before describing the manufacturing method of the present invention in detail, some terms used in the present specification are defined or described.

[0071] In this specification, unless otherwise specified, an "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound.

[0072] Examples of the "organic group" include:

[0073] an alkyl group which may have one or more substituents,

[0074] an alkenyl group which may have one or more substituents,

[0075] an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group,

[0076] Formyl,

[0077] RaO-,

[0078] RaCO-,

[0079] RaSO2-,

[0080] RaCOO-

[0081] RaNRaCO-,

[0082] RaCONRa-

[0083] RaOCO-, and

[0084] RaOSO2-

[0085] (In these formulas, Ra is independently

[0086] An alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents).

[0087] As the organic group, an alkyl group which may have one or more substituents is preferred.

[0088] In this specification, unless otherwise stated, "substituent" means a group that can be substituted. Examples of such "substituent" include: aliphatic group, aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, 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 an aliphatic amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thiol group, an aromatic thiol group, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group or a diaromatic oxyphosphinyl group.

[0089] The aliphatic group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic group include an alkyl group having a total carbon number of 1 to 8, preferably 1 to 4, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc.

[0090] The aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methylsulfonylphenyl group.

[0091] The heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the heterocyclic group include a 5- to 6-membered heterocyclic ring having a total carbon number of 2 to 12, preferably 2 to 10, such as a 2-tetrahydrofuranyl group and a 2-pyrimidinyl group.

[0092] The acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the acyl group include an acyl group having a total carbon number of 2 to 8, preferably 2 to 4, such as an acetyl group, a propionyl group, a benzoyl group, a 3-pyridinecarbonyl group, etc.

[0093] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. Examples of the acylamino group include acylamino groups having a total carbon number of 2 to 12, preferably 2 to 8, and alkylcarbonylamino groups having a total carbon number of 2 to 8, such as acetylamino groups, benzoylamino groups, 2-pyridinecarbonylamino groups, and propionylamino groups.

[0094] The aliphatic oxycarbonyl group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic oxycarbonyl group include an alkoxycarbonyl group having a total carbon number of 2 to 8, preferably 2 to 4, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, etc.

[0095] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the carbamoyl group include an unsubstituted carbamoyl group and an alkyl carbamoyl group having 2 to 9 carbon atoms in total, preferably an unsubstituted carbamoyl group and an alkyl carbamoyl group having 2 to 5 carbon atoms in total, such as N-methyl carbamoyl group, N,N-dimethyl carbamoyl group, N-phenyl carbamoyl group, etc.

[0096] The aliphatic sulfonyl group may be saturated or unsaturated, and may have a hydroxyl group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic sulfonyl group include an alkylsulfonyl group having a total carbon number of 1 to 6, preferably a total carbon number of 1 to 4, such as a methylsulfonyl group.

[0097] The aromatic sulfonyl group may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic sulfonyl group include an arylsulfonyl group having a total carbon number of 6 to 10, such as a benzenesulfonyl group.

[0098] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group or the like.

[0099] The acylamino group may include, for example, acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino, etc. Examples of the acylamino group include acylamino groups having a total carbon number of 2 to 12, preferably acylamino groups having a total carbon number of 2 to 8, and more preferably alkylcarbonylamino groups having a total carbon number of 2 to 8, such as acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino, etc.

[0100] The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, or the like.

[0101] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 total carbon atoms, a dialkylsulfamoyl group having 2 to 10 total carbon atoms, an arylsulfamoyl group having 7 to 13 total carbon atoms, and a heterocyclic sulfamoyl group having 2 to 12 total carbon atoms. More preferred examples include a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 total carbon atoms, a dialkylsulfamoyl group having 3 to 6 total carbon atoms, an arylsulfamoyl group having 6 to 11 total carbon 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, a phenylsulfamoyl group, and a 4-pyridylsulfamoyl group.

[0102] The aliphatic oxy group may be saturated or unsaturated, and may include methoxy, ethoxy, isopropoxy, cyclohexyloxy, methoxyethoxy, etc. Examples of the aliphatic oxy group include alkoxy groups having a total carbon number of 1 to 8, preferably 1 to 6, such as methoxy, ethoxy, isopropoxy, cyclohexyloxy, methoxyethoxy, etc.

[0103] The aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group condensed with the aromatic group, or an aliphatic oxycarbonyl group, and preferably may have an aliphatic group having a total carbon number of 1 to 4, an aliphatic oxy group having a total carbon number of 1 to 4, a halogen atom, a carbamoyl group having a total carbon number of 1 to 4, a nitro group, or an aliphatic oxycarbonyl group having a total carbon number of 2 to 4.

[0104] The aliphatic thiol group may be saturated or unsaturated, and examples thereof include alkylthio groups having 1 to 8 total carbon atoms, more preferably 1 to 6 total carbon atoms, such as methylthio, ethylthio, carbamoylmethylthio, tert-butylthio and the like.

[0105] The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoylamino group include carbamoylamino groups, alkylcarbamoylamino groups having 2 to 9 total carbon atoms, dialkylcarbamoylamino groups having 3 to 10 total carbon atoms, arylcarbamoylamino groups having 7 to 13 total carbon atoms, and heterocycliccarbamoylamino groups having 3 to 12 total carbon atoms. Carbamoylamino groups, alkylcarbamoylamino groups having 2 to 7 total carbon atoms, dialkylcarbamoylamino groups having 3 to 6 total carbon atoms, arylcarbamoylamino groups having 7 to 11 total carbon atoms, and heterocycliccarbamoylamino groups having 3 to 10 total carbon atoms are preferred, such as carbamoylamino groups, methylcarbamoylamino groups, N,N-dimethylcarbamoylamino groups, phenylcarbamoylamino groups, and 4-pyridylcarbamoylamino groups.

[0106] Hereinafter, the production method of the present invention will be described in detail.

[0107] Conventionally, fluorinated surfactants have been used in emulsion polymerization of fluorinated elastomers. However, fluorinated surfactants are difficult to decompose in natural environments, and emulsion polymerization using hydrocarbon surfactants that are easily decomposed in natural environments has been studied. However, in polymerization using hydrocarbon surfactants, polymer deposits on the polymerization tank increase and the reaction time becomes longer, and there is room for improvement in this regard.

[0108] The production method of the present invention is based on the following discovery: by using a hydrocarbon-based surfactant and a specific fluorine-containing compound in combination, even if a hydrocarbon-based surfactant that is easily decomposed in a natural environment is used, the amount of polymer attached to the polymerization tank is small, and a desired amount of fluorine-containing elastomer can be produced in a short time.

[0109] The method for producing a fluorine-containing elastomer of the present invention comprises the following steps: in the presence of a fluorine-containing compound (A) having a functional group capable of reacting in free radical polymerization and a hydrophilic group and a hydrocarbon surfactant (B), emulsion polymerizing a fluorine-containing monomer in an aqueous medium to obtain a fluorine-containing elastomer.

[0110] The production method of the present invention, by having the above-mentioned constitution, can reduce the polymer deposits on the polymerization tank even when a hydrocarbon-based surfactant is used, thereby shortening the reaction time. In addition, the number of fluorine-containing elastomer particles in the aqueous dispersion of the fluorine-containing elastomer obtained by polymerization can be increased, thereby improving the stability of the aqueous dispersion.

[0111] Furthermore, despite the use of a hydrocarbon-based surfactant, a fluorinated elastomer having excellent vulcanization characteristics and a fluorinated elastomer molded article (cross-linked molded article) having excellent normal physical properties can be obtained.

[0112] The fluorinated elastomer obtained by the production process of the present invention is not particularly limited, and examples thereof include copolymers of two or more fluorinated monomers, and copolymers of a fluorinated monomer and a non-fluorinated monomer.

[0113] In the present invention, fluorinated elastomer refers to an amorphous fluorinated polymer. "Amorphous" means that the size of the melting peak (ΔH) appearing in differential scanning calorimetry [DSC] (heating temperature 10°C / min) or differential thermal analysis [DTA] (heating rate 10°C / min) of the fluorinated polymer is 4.5 J / g or less. Fluorinated elastomers exhibit elastomeric properties by crosslinking. Elastomeric properties refer to the following properties: the polymer can be stretched and can maintain its original length when the force required to stretch the polymer is no longer applied.

[0114] Examples of the fluorinated monomer include vinylidene fluoride (VdF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl fluoride, iodine-containing fluorinated vinyl ether, and the general formula (2)

[0115] CHX 1 =CX 2 Rf (2)

[0116] (Where X 1 and X 2 One of them is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) or the like.

[0117] As the PAVE, perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE) are more preferred, and PMVE is particularly preferred.

[0118] Alternatively, as the above PAVE, the formula: CF2=CFOCF2ORf c (Where Rf c The fluorocarbon is a perfluorovinyl ether represented by a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. For example, CF2=CFOCF2OCF3, CF2=CFOCF2OCF2CF3 or CF2=CFOCF2OCF2CF2OCF3 is preferably used.

[0119] As the fluorine-containing monomer represented by the above formula (2), a monomer in which Rf is a linear fluoroalkyl group is preferred, and a monomer in which Rf is a linear perfluoroalkyl group is more preferred. The number of carbon atoms of Rf is preferably 1 to 6.

[0120] Examples of the fluorine-containing monomer represented by the above formula (2) include CH2=CFCF3, CH2=CFCF2CF3, CH2=CFCF2CF2CF3, CH2=CFCF2CF2CF2CF3, CHF=CHCF3 (1,3,3,3-tetrafluoropropylene), etc. Among them, 2,3,3,3-tetrafluoropropylene represented by CH2=CFCF3 is preferred.

[0121] As the above-mentioned non-fluorine-containing monomers, there can be mentioned, for example, α-olefin monomers having 2 to 10 carbon atoms, such as ethylene, propylene, butene, pentene, etc.; alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group, such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, butyl vinyl ether, etc.; and one or more of these monomers or compounds can be used in combination.

[0122] As the above-mentioned fluorinated elastomer, a fluorinated elastomer containing -CH2- in the main chain is preferred. As the fluorinated elastomer containing -CH2- in the main chain, the fluorinated elastomer described below can be cited. As the fluorinated elastomer containing -CH2- in the main chain, there is no particular limitation as long as it contains the chemical structure shown by -CH2-, and for example, elastomers containing structures such as -CH2-CF2-, -CH2-CH(CH3)-, and -CH2-CH2- can be cited, which can be introduced into the main chain of the fluorinated elastomer by, for example, polymerizing vinylidene fluoride, propylene, ethylene, etc.

[0123] The fluorine-containing elastomer preferably comprises, for example, tetrafluoroethylene (TFE), vinylidene fluoride (VdF) and the following formula (1):

[0124] CF2=CF-Rf a (1)

[0125] (Where Rf a-CF3 or -ORf b (Rf b It is a structural unit of at least one monomer selected from the group consisting of a perfluoroethylenically unsaturated compound represented by a perfluoroalkyl group having 1 to 5 carbon atoms (for example, hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), etc.).

[0126] More specifically, the fluorinated elastomers include VdF fluorinated elastomers, TFE / propylene (Pr) fluorinated elastomers, TFE / Pr / VdF fluorinated elastomers, ethylene (Et) / HFP fluorinated elastomers, Et / HFP / VdF fluorinated elastomers, Et / HFP / TFE fluorinated elastomers, Et / TFE / PAVE fluorinated elastomers, etc. Among these, VdF fluorinated elastomers, TFE / Pr fluorinated elastomers, TFE / Pr / VdF fluorinated elastomers, or Et / TFE / PAVE fluorinated elastomers are more preferred in terms of good heat aging resistance and oil resistance.

[0127] The VdF-based fluorinated elastomer is a fluorinated elastomer having VdF units. In the VdF-based fluorinated elastomer, the VdF units are preferably 20 mol% to 90 mol% of the total molar number of the VdF units and monomer units derived from other monomers, more preferably 40 mol% to 85 mol%, further preferably 45 mol% to 80 mol%, particularly preferably 50 mol% to 80 mol%.

[0128] Furthermore, other monomers in the VdF-based fluorinated elastomer are not particularly limited as long as they are copolymerizable with VdF, and for example, the above-mentioned fluorinated monomers can be used.

[0129] As the above-mentioned VdF-based fluorine-containing elastomer, it is preferred to have at least one copolymer selected from the group consisting of a VdF / HFP copolymer, a VdF / TFE / HFP copolymer, a VdF / CTFE copolymer, a VdF / CTFE / TFE copolymer, a VdF / PAVE copolymer, a VdF / TFE / PAVE copolymer, a VdF / HFP / PAVE copolymer, a VdF / HFP / TFE / PAVE copolymer, a VdF / TFE / Pr copolymer, a VdF / Et / HFP copolymer, and a VdF / copolymer of a fluorine-containing monomer represented by formula (2). In addition, as other monomers other than VdF, it is more preferred to have at least one monomer selected from the group consisting of TFE, HFP and PAVE.

[0130] Among them, at least one copolymer selected from the group consisting of VdF / HFP copolymers, VdF / TFE / HFP copolymers, VdF / copolymers of fluorinated monomers represented by formula (2), VdF / PAVE copolymers, VdF / TFE / PAVE copolymers, VdF / HFP / PAVE copolymers, and VdF / HFP / TFE / PAVE copolymers is preferred, and at least one copolymer selected from the group consisting of VdF / HFP copolymers, VdF / HFP / TFE copolymers, VdF / copolymers of fluorinated monomers represented by formula (2), and VdF / PAVE copolymers is more preferred.

[0131] As the VdF / PAVE copolymer, a copolymer having a VdF / PAVE composition of (65 to 90) / (35 to 10) (mol %) is preferred.

[0132] In addition, it is also one of the preferred embodiments that the composition of VdF / PAVE is (50 to 78) / (50 to 22) (mol %).

[0133] As the VdF / TFE / PAVE copolymer, a copolymer having a composition of VdF / TFE / PAVE of (40 to 80) / (3 to 40) / (15 to 35) (mol %) is preferred.

[0134] As the VdF / HFP / PAVE copolymer, a copolymer having a composition of VdF / HFP / PAVE of (65 to 90) / (3 to 25) / (3 to 25) (mol %) is preferred.

[0135] The VdF / HFP / TFE / PAVE copolymer preferably has a composition of (40-90) / (0-25) / (0-40) / (3-35) (mol %) of VdF / HFP / TFE / PAVE, and more preferably has a composition of (40-80) / (3-25) / (3-40) / (3-25) (mol %).

[0136] As the VdF / fluorinated monomer (2) copolymer represented by formula (2), it is preferred that the VdF / fluorinated monomer (2) unit is (85-20) / (15-80) (mol%), and the monomer units other than VdF and the fluorinated monomer (2) are 0-50 mol% of the total monomer units. The mol% ratio of the VdF / fluorinated monomer (2) unit is more preferably (80-20) / (20-80). In addition, it is also preferred that the composition of the VdF / fluorinated monomer (2) unit is (78-50) / (22-50) (mol%).

[0137] It is also preferred that the ratio of VdF / fluorinated monomer (2) units is (85 to 50) / (15 to 50) (mol%), and that monomer units other than VdF and the fluorinated monomer (2) account for 1 to 50 mol% of the total monomer units. As monomers other than VdF and the fluorinated monomer (2), monomers exemplified as other monomers in the above-mentioned VdF-based fluorinated elastomers, such as TFE, HFP, PMVE, perfluoroethylvinyl ether (PEVE), PPVE, CTFE, trifluoroethylene, hexafluoroisobutylene, vinyl fluoride, Et, Pr, alkyl vinyl ether, and monomers providing crosslinking groups are preferred, and PMVE, CTFE, HFP, and TFE are more preferred.

[0138] The TFE / Pr-based fluorinated elastomer is a fluorinated copolymer composed of 45 mol% to 70 mol% of TFE and 55 mol% to 30 mol% of Pr. In addition to these two components, a specific third component may be contained.

[0139] As the specific third component, for example, fluorinated monomers such as fluorinated olefins other than TFE (for example, VdF, HFP, CTFE, perfluoro(butylethylene) etc.), fluorinated vinyl ethers (perfluoro(propyl vinyl ether), perfluoro(methyl vinyl ether) etc.), α-olefins (ethylene, 1-butene etc.), vinyl ethers (ethyl vinyl ether, butyl vinyl ether, hydroxybutyl vinyl ether etc.), vinyl esters (vinyl acetate, vinyl benzoate, vinyl crotonate, vinyl methacrylate etc.), hydrocarbon monomers, etc. may be included. The specific third component may be one kind or two or more kinds may be used in combination.

[0140] The TFE / Pr-based fluorinated elastomer preferably contains VdF. Among the TFE / Pr-based fluorinated elastomers, an elastomer composed of TFE, Pr and VdF is referred to as a TFE / Pr / VdF-based fluorinated elastomer.

[0141] The TFE / Pr / VdF-based fluorinated elastomer may further contain the above-mentioned specific third component in addition to VdF. The above-mentioned specific third component may be used alone or in combination of two or more.

[0142] The total content of the third component in the TFE / Pr-based fluorinated elastomer is preferably 35 mol % or less, more preferably 33 mol % or less, further preferably 31 mol % or less.

[0143] As the Et / HFP copolymer, the composition of Et / HFP is preferably (35 to 80) / (65 to 20) (mol %), and more preferably (40 to 75) / (60 to 25) (mol %).

[0144] In the Et / HFP / TFE copolymer, the composition of Et / HFP / TFE is preferably (35 to 75) / (25 to 50) / (0 to 15) (mol %), and more preferably (45 to 75) / (25 to 45) / (0 to 10) (mol %).

[0145] In the Et / TFE / PAVE copolymer, the composition of Et / TFE / PAVE is preferably (10-40) / (32-60) / (20-40) (mol %), and more preferably (20-40) / (40-50) / (20-30) (mol %). As PAVE, PMVE is preferred.

[0146] The fluorine-containing elastomer preferably contains a VdF unit, and a VdF / HFP copolymer or a VdF / HFP / TFE copolymer is particularly preferred. For example, a copolymer having a composition of (32 to 85) / (10 to 34) / (0 to 34) (mol %) of VdF / HFP / TFE is particularly preferred. The composition of VdF / HFP / TFE is more preferably (32 to 85) / (15 to 34) / (0 to 34) (mol %), and further preferably (47 to 81) / (17 to 29) / (0 to 26) (mol %).

[0147] For example, in the above-mentioned VdF / HFP copolymer, the composition of VdF / HFP is preferably (45-85) / (15-55) (mol %), more preferably (50-83) / (17-50) (mol %), further preferably (55-81) / (19-45) (mol %), and still more preferably (60-80) / (20-40) (mol %).

[0148] In the above-mentioned VdF / HFP / TFE copolymer, the composition of VdF / HFP / TFE is preferably (32 to 80) / (10 to 34) / (4 to 34) (mol %).

[0149] The fluorinated elastomer contains preferably 0.001 to 3.0 mol %, more preferably 0.005 to 2.0 mol %, further preferably 0.01 to 1.5 mol % of the structural units based on all monomer units.

[0150] The content of the structural unit derived from the fluorine-containing compound (A) can be determined based on 19 F-NMR and 1 The measurement is performed by calculation based on the measured values ​​in H-NMR, elemental analysis, etc.

[0151] The substances exemplified as the above-mentioned fluorine-containing elastomers are those composed of main monomers, and substances obtained by copolymerizing monomers providing crosslinking groups can be used. As monomers providing crosslinking groups, any monomer can be used as long as appropriate crosslinking groups can be introduced according to the production method or the crosslinking system, and examples thereof include known polymerizable compounds containing crosslinking groups such as iodine atoms, bromine atoms, carbon-carbon double bonds, cyano groups, carboxyl groups, hydroxyl groups, amino groups, and ester groups.

[0152] Preferred examples of the monomer providing a crosslinkable group include compounds represented by the general formula (3).

[0153] CY 1 2=CY 2 R f 2 X 1 (3)

[0154] (Where Y 1 , Y 2 is a fluorine atom, a hydrogen atom or -CH3; R f 2 X is a linear or branched fluorine-containing alkylene group which may have one or more ether-bonded oxygen atoms, may have an aromatic ring, and in which a part or all of the hydrogen atoms are substituted by fluorine atoms; 1 is an iodine atom or a bromine atom. )

[0155] Specific examples of the monomer providing a crosslinkable group include iodine- or bromine-containing monomers represented by general formula (4) and iodine- or bromine-containing monomers represented by general formulae (5) to (22). These monomers can be used alone or in any combination.

[0156] CY 1 2=CY 2 R f 3 CHR 1 -X 1 (4)

[0157] (Where Y 1 , Y 2 , X 1 Same as above, R f 3 is a linear or branched fluorinated alkylene group which may have one or more ether-bonded oxygen atoms and in which a part or all of the hydrogen atoms are substituted with fluorine atoms, that is, a linear or branched fluorinated alkylene group in which a part or all of the hydrogen atoms are substituted with fluorine atoms, a linear or branched fluorinated oxyalkylene group in which a part or all of the hydrogen atoms are substituted with fluorine atoms, or a linear or branched fluorinated polyoxyalkylene group in which a part or all of the hydrogen atoms are substituted with fluorine atoms; R 1 is a hydrogen atom or a methyl group)

[0158] CY 4 2=CY 4 (CF2) n -X 1 (5)

[0159] (Where Y 4 are the same or different, are hydrogen atoms or fluorine atoms, and n is an integer from 1 to 8)

[0160] CF2=CFCF2R f 4 -X 1 (6)

[0161] (Where R 4 -(OCF2) n -or-(OCF(CF3)) n -, n is an integer from 0 to 5)

[0162] CF2=CFCF2(OCF(CF3)CF2) m (OCH2CF2CF2) n OCH2CF2-X 1 (7)

[0163] (wherein m is an integer from 0 to 5, and n is an integer from 0 to 5)

[0164] CF2=CFCF2(OCH2CF2CF2) m (OCF(CF3)CF2) n OCF(CF3)-X 1 (8)

[0165] (wherein m is an integer from 0 to 5, and n is an integer from 0 to 5)

[0166] CF2=CF(OCF2CF(CF3)) m O(CF2) n -X 1 (9)

[0167] (wherein m is an integer from 0 to 5, and n is an integer from 1 to 8)

[0168] CF2=CF(OCF2CF(CF3)) m -X 1 (10)

[0169] (wherein m is an integer from 1 to 5)

[0170] CF2=CFOCF2(CF(CF3)OCF2) n CF(-X 1)CF3 (11)

[0171] (where n is an integer from 1 to 4)

[0172] CF2=CFO(CF2) n OCF(CF3)-X 1 (12)

[0173] (where n is an integer from 2 to 5)

[0174] CF2=CFO(CF2) n -(C6H4)-X 1 (13)

[0175] (where n is an integer from 1 to 6)

[0176] CF2=CF(OCF2CF(CF3)) n OCF2CF(CF3)-X 1 (14)

[0177] (where n is an integer from 1 to 2)

[0178] CH2=CFCF2O(CF(CF3)CF2O) n CF(CF3)-X 1 (15)

[0179] (where n is an integer from 0 to 5)

[0180] CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 1 (16)

[0181] (wherein m is an integer from 0 to 5, and n is an integer from 1 to 3)

[0182] CH2=CFCF2OCF(CF3)OCF(CF3)-X 1 (17)

[0183] CH2=CFCF2OCH2CF2-X 1 (18)

[0184] CF2=CFO(CF2CF(CF3)O) m CF2CF(CF3)-X 1 (19)

[0185] (wherein m is an integer greater than 0)

[0186] CF2=CFOCF(CF3)CF2O(CF2)n -X 1 (20)

[0187] (where n is an integer greater than 1)

[0188] CF2=CFOCF2OCF2CF(CF3)OCF2-X 1 (twenty one)

[0189] CH2=CH-(CF2) n X 1 (twenty two)

[0190] (where n is an integer from 2 to 8)

[0191] (In general formulas (5) to (22), X 1 Same as above)

[0192] As the iodine- or bromine-containing monomer represented by the general formula (4), preferably, there can be mentioned an iodine-containing fluorinated vinyl ether represented by the general formula (23):

[0193] [Chemistry 1]

[0194]

[0195] (wherein m is an integer from 1 to 5, and n is an integer from 0 to 3)

[0196] More specifically, we can cite

[0197] [Chemistry 2]

[0198] ICH2CF2CF2OCF=CF2、I(CH2CF2CF2O)2CF=CF2、

[0199] I(CH2CF2CF2O)3CF=CF2,

[0200]

[0201] etc. Among these, ICH2CF2CF2OCF=CF2 is preferred.

[0202] More specifically, preferred examples of the iodine- or bromine-containing monomer represented by the general formula (5) include ICF2CF2CF=CH2 and I(CF2CF2)2CF=CH2.

[0203] More specifically, the iodine- or bromine-containing monomer represented by the general formula (9) is preferably I(CF2CF2)2OCF=CF2.

[0204] More specifically, preferred examples of the iodine- or bromine-containing monomer represented by the general formula (22) include CH2=CHCF2CF2I and I(CF2CF2)2CH=CH2.

[0205] In addition, the formula: R 2 R 3 C=CR 4 -Z-CR 5 =CR 6 R 7

[0206] (Where R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The same or different, all of which are H, or an alkyl group having 1 to 5 carbon atoms; Z is a linear or branched alkylene or cycloalkylene group having 1 to 18 carbon atoms which may contain an oxygen atom and is preferably at least partially fluorinated, or a (per)fluoropolyoxyalkylene group) is also preferably used as a monomer providing a crosslinking group. It should be noted that in this specification, the so-called "(per)fluoropolyoxyalkylene group" means "fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group".

[0207] Z is preferably a (per)fluoroalkylene group having 4 to 12 carbon atoms, 2 , R 3 , R 4 , R 5 , R 6 and R 7 Preferred is a hydrogen atom.

[0208] When Z is a (per)fluoropolyoxyalkylene group, preferably, the formula:

[0209] -(Q) p -CF2O-(CF2CF2O) m -(CF2O) n -CF2-(Q) p -

[0210] (wherein, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, m and n are integers such that the m / n ratio is 0.2 to 5 and the molecular weight of the (per)fluoropolyoxyalkylene group is 500 to 10,000, preferably 1,000 to 4,000.) In the formula, Q is preferably selected from -CH2OCH2- and -CH2O(CH2CH2O) s Select CH2-(s=1~3).

[0211] Preferred dienes include:

[0212] CH2=CH-(CF2)2-CH=CH2,

[0213] CH2=CH-(CF2)4-CH=CH2,

[0214] CH2=CH-(CF2)6-CH=CH2,

[0215] Formula: CH2=CH-Z 1 -CH=CH2

[0216] (Where Z 1 -CH2OCH2-CF2O-(CF2CF2O) m -(CF2O) n -CF2-CH2OCH2- (m / n is 0.5, molecular weight is preferably 2000) and the like.

[0217] Among them, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,9-decadiene represented by CH2=CH-(CF2)6-CH=CH2 is preferred.

[0218] The number average molecular weight Mn of the fluorinated elastomer is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 500,000, particularly preferably from 20,000 to 300,000.

[0219] The fluorine content of the fluorine-containing elastomer is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. The upper limit of the fluorine content is preferably 75% by mass or less, and more preferably 73% by mass or less.

[0220] The above fluorine content is based on 19 F-NMR and 1 The measured values ​​in H-NMR, elemental analysis, etc. were calculated.

[0221] The Mooney viscosity of the fluorine-containing elastomer at 100° C. is preferably 130 or less. The Mooney viscosity is more preferably 110 or less, and further preferably 90 or less. Furthermore, the Mooney viscosity is more preferably 10 or more, and further preferably 20 or more. Here, the Mooney viscosity is a value measured in accordance with JIS K 6300-1.2013.

[0222] The glass transition temperature of the fluorinated elastomer is preferably -50°C to 0°C. The glass transition temperature is more preferably -2°C or less, and further preferably -3°C or less. In addition, the glass transition temperature is more preferably -45°C or more, and further preferably -40°C or more. The glass transition temperature may be -10°C or more, or -9°C or more. Here, the glass transition temperature can be obtained as follows: using a differential scanning calorimeter (e.g., X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.), by heating 10 mg of a sample at 20°C / min to obtain a DSC curve, the glass transition temperature can be obtained from the DSC differential curve according to JIS K 6240:2011.

[0223] The iodine content of the fluorinated elastomer is preferably 0.05 to 1.0 mass %, more preferably 0.08 mass % or more, further preferably 0.10 mass % or more, and more preferably 0.8 mass % or less, further preferably 0.60 mass % or less.

[0224] The above iodine content can be obtained by elemental analysis.

[0225] Specifically, 5 mg of Na2SO3 was mixed with 12 mg of fluorine-containing elastomer, 30 mg of a substance obtained by mixing Na2CO3 and K2CO3 at a mass ratio of 1:1 was dissolved in 20 ml of pure water to obtain an absorption liquid, and the absorption liquid was burned in oxygen in a quartz flask, and after standing for 30 minutes, it can be measured using a Shimadzu 20A ion chromatograph. As a calibration curve, a KI standard solution, a solution containing 0.5 ppm of iodide ions, and a solution containing 1.0 ppm of iodide ions can be used.

[0226] As the fluorinated monomer in the method for producing the fluorinated elastomer of the present invention, the fluorinated monomers described in connection with the above-mentioned fluorinated elastomer can be appropriately used.

[0227] The method for producing a fluorine-containing elastomer of the present invention comprises the following steps: in the presence of a fluorine-containing compound (A) having a functional group capable of reacting in free radical polymerization and a hydrophilic group and a hydrocarbon surfactant (B), emulsion polymerizing a fluorine-containing monomer in an aqueous medium to obtain a fluorine-containing elastomer.

[0228] The fluorine-containing compound (A) is preferably a compound containing an anionic or nonionic hydrophilic group, and more preferably a compound containing an anionic hydrophilic group.

[0229] For example, the fluorine-containing compound (A) may contain only anionic hydrophilic groups or only nonionic hydrophilic groups.

[0230] In addition, as the above-mentioned fluorine-containing compound (A), only a compound containing anionic hydrophilic groups may be used, only a compound containing nonionic hydrophilic groups may be used, or a compound containing anionic hydrophilic groups and a compound containing nonionic hydrophilic groups may be used in combination.

[0231] Examples of the hydrophilic group in the fluorinated compound (A) include -NH2, -PO3M (-P(O)(OM)2), -OPO3M (-OP(O)(OM)2), -SO3M, -OSO3M, -COOM, -B(OM)2, -OB(OM)2 (wherein M is H, a metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 As the hydrophilic group, -SO3M or -COOM is preferred, and -COOM is more preferred. As R 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 The most preferred alkyl group is H.

[0232] When two M's are contained in each formula, the two M's may be the same or different. Examples of the metal atom include monovalent or divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and preferably Na, K or Li.

[0233] Examples of the "functional group capable of reacting in radical polymerization" in the fluorine-containing compound (A) include a group containing a radically polymerizable unsaturated bond.

[0234] Examples of the group having a free radical polymerizable unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond can be represented by the following formula:

[0235] CX e X g =CX f R-

[0236] (Where X e , X f and X g Each independently represents F, Cl, H, CF3, CF2H, CFH2 or CH3; R represents a linking group). Examples of the linking group of R include the following R a Preferred examples include -CH=CH2, -CF=CH2、 -CH=CF 2、 Groups having unsaturated bonds such as -CF=CF2, -CH2-CH=CH2, -CF2-CF=CH2, -CF2-CF=CF2, -(C=O)-CH=CH2, -(C=O)-CF=CH2, -(C=O)-CH=CF2, -(C=O)-CF=CF2, -(C=O)-C(CH3)=CH2, -(C=O)-C(CF3)=CH2, -(C=O)-C(CH3)=CF2, -(C=O)-C(CF3)=CF2, -O-CH2-CH=CH2, -O-CF2-CF=CH2, -O-CH2-CH=CF2, -O-CF=CF2, and -O-CF2-CF=CF2.

[0237] Since the fluorinated compound (A) has a functional group that can react in free radical polymerization, it is presumed that if used in the polymerization, it reacts with the fluorinated monomer in the initial stage of the polymerization reaction, and has a hydrophilic group derived from the fluorinated compound (A), and can form particles with high stability. Therefore, it is believed that if polymerization is carried out in the presence of the fluorinated compound (A), the number of particles of the fluorinated elastomer generated during polymerization increases.

[0238] In the emulsion polymerization, the fluorinated compound (A) may be present alone or in combination of two or more.

[0239] The fluorine-containing compound (A) is preferably a compound represented by the general formula (A).

[0240] CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (A)

[0241] (Where X i , X j and X k Each independently represents F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a connecting group; Z 1 and Z 2 Each independently represents H, F or CF3, and k represents 0 or 1. i , X k , X j , R a , Z 1 and Z 2 At least one of them contains a fluorine atom. Wherein, when k is 0, Ra is a connecting group other than a single bond. )

[0242] Examples of the hydrophilic group include -NH2, -PO3M (-P(O)(OM)2), -OPO3M (-OP(O)(OM)2), -SO3M, -OSO3M, -COOM, -B(OM)2, -OB(OM)2 (wherein M is H, a metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 As the hydrophilic group, -SO3M or -COOM is preferred, and -COOM is more preferred. As R 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 The most preferred alkyl group is H.

[0243] Examples of the metal atom include monovalent or divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0244] By using the fluorinated compound (A), even though a hydrocarbon-based surfactant is used, less polymer is deposited on the polymerization tank, and the reaction time can be shortened. In addition, an aqueous dispersion having a smaller average primary particle size and better stability can be obtained.

[0245] The above R a is a linking group. In this specification, "linking group" refers to a divalent linking group. The linking group may be a single bond, preferably containing at least one carbon atom. Where k is 0, R a The connecting group other than a single bond is preferably a group containing at least 1 carbon atom. The number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. The upper limit is not limited, for example, it may be 100 or less, or 50 or less.

[0246] The linking group may be a chain or branched, cyclic or acyclic structure, saturated or unsaturated, substituted or unsubstituted, and may contain one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as desired, and may contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, carbamate, urea and carbamate as desired. The linking group does not contain carbon atoms and may be a chain heteroatom such as oxygen, sulfur or nitrogen.

[0247] The above R a Preferred are, for example, chain heteroatoms such as oxygen, sulfur, and nitrogen, or divalent organic groups.

[0248] R a In the case of a divalent organic group, the hydrogen atom bonded to the carbon atom may be substituted by a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. a It may be in the form of a chain or a branched chain, or in the form of a ring or an acyclic ring. a Functional groups (eg, ester, ether, ketone, amine, halide, etc.) may be included.

[0249] In addition, R a It may be a non-fluorinated divalent organic group or a partially fluorinated or perfluorinated divalent organic group.

[0250] As R a , and can be, for example: a hydrocarbon group in which no fluorine atoms are bonded to the carbon atom; a hydrocarbon group in which a part of the hydrogen atoms bonded to the carbon atom are substituted by fluorine atoms; a hydrocarbon group in which all the hydrogen atoms bonded to the carbon atom are substituted by fluorine atoms, a hydrocarbon group containing -(C=O)-, -(C=O)-O- or -(C=O)-, which may contain oxygen atoms, may contain double bonds, and may contain functional groups.

[0251] R a Preferably, it is a hydrocarbon group having 1 to 100 carbon atoms which may contain -(C=O)-, -(C=O)-O- or an ether bond and may contain a carbonyl group, and a part or all of the hydrogen atoms bonded to the carbon atoms in the hydrocarbon group may be substituted with fluorine.

[0252] As R a , preferably selected from -(CH2) a -、-(CF2) a -、-O-(CF2) a -、-(CF2) a -O-(CF2) b -、-O(CF2) a -O-(CF2) b -、-(CF2) a -[O-(CF2) b ] c -、-O(CF2) a -[O-(CF2) b ] c -、-[(CF2) a -O] b -[(CF2) c -O] d -、-O[(CF2) a -O]b -[(CF2) c -O] d -、-O-[CF2CF(CF3)O] a -(CF2) b -, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2) a -、-(C=O)-(CF2) a -、-(C=O)-O-(CH2) a -、-(C=O)-O-(CF2) a -、-(C=O)-[(CH2) a -O] b -、-(C=O)-[(CF2) a -O] b -、-(C=O)-O[(CH2) a -O] b -、-(C=O)-O[(CF2) a -O] b -、-(C=O)-O[(CH2) a -O] b -(CH2) c -、-(C=O)-O[(CF2) a -O] b -(CF2) c -、-(C=O)-(CH2) a -O-(CH2) b -、-(C=O)-(CF2) a -O-(CF2) b -、-(C=O)-O-(CH2) a -O-(CH2) b -、-(C=O)-O-(CF2) a -O-(CF2) b At least one of -, -(C=O)-O-C6H4- and combinations thereof.

[0253] In the formula, a, b, c and d are independently at least 1. a, b, c and d can independently be 2 or more, 3 or more, 4 or more, 10 or more, or 20 or more. The upper limit of a, b, c and d is, for example, 100.

[0254] As R aPreferred specific examples include -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CH2-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -、-(C=O)-[(CF2)2-O] n -、-(C=O)-O[(CH2)2-O] n -、-(C=O)-O[(CF2)2-O] n -、-(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-(CH2)2-O-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-, -(C=O)-O-(CF2)2-O-(CF2)-, -(C=O)-O-C6H4-, etc. Specifically, the above R a Preferably -CF2-O-, -CF2-O-CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, -CF2-O- CF(CF3)CF2-O-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-O-(CH2)-, -(C=O)-O[(CH2)2-O] n -、-(C=O)-O[(CH2)2-O] n -(CH2)-, -(C=O)-(CH2)2-O-(CH2)- or -(C=O)-O-C6H4-.

[0255] In the above formula, n is an integer of 1-10.

[0256] As -R in the above general formula (A) a -(CZ 1 Z 2 ) k, preferably -CF2-O-CF2-, -CF2-O-CF(CF3)-, -CF2-O-C(CF3)2-, -CF2-O-CF2-CF2-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2-C(CF3)2-, -CF2-O-CF2CF2-CF2-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF2CF2-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)-CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)CF2-CF2-, -CF2-O-CF(CF3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-C(CF3)2-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-C(CF3)2-, -(C=O)-, -(C=O)-O-, -(C=O)-(CH2)-, -(C=O)-(CF2)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CF2)-, -(C=O)-[(CH2)2-O] n -(CH2)-, -(C=O)-[(CF2)2-O] n -(CF2)-, -(C=O)-[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-[(CF2)2-O] n -(CF2)-(CF2)-, -(C=O)-O[(CH2)2-O] n -(CF2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O[(CF2)2-O] n -(CF2)-, -(C=O)-O[(CF2)2-O] n-(CF2)-(CF2)-, -(C=O)-(CH2)2-O-(CH2)-(CH2)-, -(C=O)-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-(CH2)-, -(C= O)-O-(CF2)2-O-(CF2)-(CF2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2-, -(C=O)-O-(CF2)2-O-(CF2)-C(CF3)2- or -(C=O)-O-C6H4- C(CF3)2-, more preferably -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF 3)CF2-CF(CF3)-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, -(C=O)-, -(C=O)-O-(CH2)-, -(C=O)-O-(CH2)-(CH2)-, -(C=O)-O[(CH2)2-O] n -(CH2)-(CH2)-, -(C=O)-O-(CH2)2-O-(CH2)-C(CF3)2- or -(C=O)-O-C6H4-C(CF3)2-.

[0257] In the above formula, n is an integer of 1-10.

[0258] Specific examples of the compound represented by the general formula (A) include:

[0259] [Chemistry 3]

[0260]

[0261] (Where X j and Y 3 Same as above. n is an integer from 1 to 10) and the like.

[0262] As R a , preferably a divalent group represented by the following general formula (r1),

[0263] -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -(r1)

[0264] (Where X 6Each independently represents H, F or CF3, e represents an integer from 0 to 3, f represents an integer from 0 to 3, g represents 0 or 1, h represents 0 or 1, and i represents 0 or 1),

[0265] A divalent group represented by the following general formula (r2) is also preferred.

[0266] -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g -(r2)

[0267] (Where X 7 Each is independently H, F or CF3, e is an integer from 0 to 3, g is 0 or 1, h is 0 or 1, and i is 0 or 1.)

[0268] In addition, as -R in the above general formula (A) a -(CZ 1 Z 2 ) k -, the following formula (t1) is also preferred:

[0269] -(C=O) h -(O) i -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 -(t1)

[0270] (Where X 6 Each independently represents H, F or CF3, e represents an integer of 0 to 3, f represents an integer of 0 to 3, g represents 0 or 1, h represents 0 or 1, i represents 0 or 1, Z 1 and Z 2 Each independently represents a divalent group represented by F or CF3, wherein Z 1 and Z 2 More preferably, one is F and the other is CF3. a -(CZ 1 Z 2 ) k -, the following formula (t2) is also preferred:

[0271] -(C=O) h -(O) i -CF2-O-(CX 7 2) e -(O) g -CZ1 Z 2 -(t2)

[0272] (Where X 7 Each independently represents H, F or CF3, e represents an integer from 0 to 3, g represents 0 or 1, h represents 0 or 1, i represents 0 or 1, Z 1 and Z 2 Each independently represents a divalent group represented by H, F or CF3, in formula (t2), Z 1 and Z 2 More preferably, one is F and the other is CF3.

[0273] The compound represented by the general formula (A) also preferably has, in addition to the hydrophilic group (Y 3 ) has a CF bond and does not have a CH bond. That is, in the general formula (A), preferably X i , X j and X k All are F, R a The perfluoroalkylene group may have 1 or more carbon atoms, and the perfluoroalkylene group may be any of a chain or branched chain, cyclic or acyclic, and may contain at least one chain heteroatom. The perfluoroalkylene group may have 2 to 20 carbon atoms, or 4 to 18 carbon atoms.

[0274] The compound represented by the general formula (A) may also be partially fluorinated. That is, the compound represented by the general formula (A) also preferably has, in addition to the hydrophilic group (Y 3 ) has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0275] The compound represented by the general formula (A) is preferably a compound represented by the following formula (Aa).

[0276] CF2=CF-O-Rf 0 -Y 3 (Aa)

[0277] (Where Y 3 is a hydrophilic group, Rf 0 It is perfluorinated and may be chain or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and is a perfluorinated divalent linking group that optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen.

[0278] The compound represented by the general formula (A) is preferably a compound represented by the following formula (Ab).

[0279] CH2=CH-O-Rf 0 -Y 3 (Ab)

[0280] (Where Y 3 is a hydrophilic group, Rf 0 is a perfluorinated divalent linking group defined by formula (Aa).

[0281] In the general formula (A), Y 3 -OSO3M is one of the preferred methods. 3 In the case of -OSO3M, examples of the compound represented by the general formula (A) include CF2=CF(OCF2CF2CH2OSO3M), CH2=CH((CF2)4CH2OSO3M), CF2=CF(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF(CF3)CH2OSO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M), CH2=CH((CF2)4CH2OSO3M), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(CF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M), and CH2=CH(CF2CF2CH2OSO3M). In the above formula, M is the same as above.

[0282] In the general formula (A), Y 3 -SO3M is also one of the preferred methods. 3 In the case of -SO3M, examples of the compound represented by the general formula (A) include CF2=CF(OCF2CF2SO3M), CF2=CF(O(CF2)4SO3M), CF2=CF(OCF2CF(CF3)SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M), CH2=CH(CF2CF2SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M), CH2=CH((CF2)4SO3M), CH2=CH((CF2)3SO3M), etc. In the above formula, M is the same as above.

[0283] In the general formula (A), Y 3 -COOM is also one of the preferred methods. 3 In the case of -COOM, examples of the compound represented by the general formula (A) include CF2=CF(OCF2CF2COOM), CF2=CF(OCF2CF2CF2COOM), CF2=CF(O(CF2)5COOM), CF2=CF(OCF2CF(CF3)COOM), CF2=CF(OCF2CF(CF3)O(CF2)n COOM) (n is greater than 1), CH2=CH(CF2CF2COOM), CH2=CH((CF2)4COOM), CH2=CH((CF2)3COOM), CF2=CF(OCF2CF2SO2NR' CH2COOM), CF2=CF(O(CF2)4SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)O CF2CF2SO2NR'CH2COOM), CH2=CH(CF2CF2SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR'CH2C OOM), CH2=CH((CF2)4SO2NR'CH2COOM), CH2=CH(CF2CF2SO2NR'CH2COOM), CH2=CH((CF2)3SO2NR'CH2COOM), etc. In the above formula, R' is H or C 1-4 The alkyl group and M are the same as described above.

[0284] In the general formula (A), Y 3 -OPO3M(-OP(O)(OM)2) is also one of the preferred methods. 3 In the case of -OPO3M, examples of the compound represented by the general formula (A) include CF2=CF(OCF2CF2CH2OP(O)(OM)2), CF2=CF(O(CF2)4CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CH2=CH(CF2CF2CH2OP(O)(OM)2, CH2=CH((CF2)4CH2OP(O)(OM)2), CH2=CH((CF2)3CH2OP(O)(OM)2), etc. In the above formula, M is the same as above.

[0285] In the general formula (A), Y 3 -PO3M(-P(O)(OM)2) is also one of the preferred methods. 3In the case of -PO3M, the compound represented by the general formula (A) may include CF2=CF(OCF2CF2P(O)(OM)2), CF2=CF(O(CF2)4P(O)(OM)2), CF2=CF(OCF2CF(CF3)P(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2), CH2=CH(CF2CF2P(O)(OM)2), CH2=CH((CF2)4P(O)(OM)2), CH2=CH((CF2)3P(O)(OM)2), etc., wherein M is the same as above.

[0286] The compound represented by the general formula (4) is preferably at least one selected from the group consisting of the following monomers, wherein the monomer is represented by the following general formula (5):

[0287] CX2=CY(-CZ2-O-Rf-Y 3 ) (5)

[0288] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Z is the same or different and is -H, -F, an alkyl group or a fluorinated alkyl group. Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond. Y 3 Same as above); the following general formula (6):

[0289] CX2=CY(-O-Rf-Y 3 ) (6)

[0290] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. 3 Same as above); and the following general formula (7):

[0291] CX2=CY(-Rf-Y 3 ) (7)

[0292] (wherein, X is the same or different and is -H or -F, Y is -H, -F, an alkyl group or a fluorinated alkyl group, and Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms. 3 Same as above) shown in the monomer.

[0293] The fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond is an alkylene group having no structure with an oxygen atom at the end and having an ether bond between carbon atoms.

[0294] In the above general formula (5), X is -H or -F. Both 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.

[0295] In the above general formula (5), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group.

[0296] The alkyl group is an alkyl group not containing fluorine atoms and may have at least 1 carbon atom. The alkyl group may have preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms.

[0297] The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0298] As the above-mentioned Y, -H, -F or -CF3 is preferred, and -F is more preferred.

[0299] In the above general formula (5), Z is the same or different and is -H, -F, alkyl or fluoroalkyl.

[0300] The alkyl group is an alkyl group not containing fluorine atoms and may have at least 1 carbon atom. The alkyl group may have preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms.

[0301] The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0302] As the above-mentioned Z, -H, -F or -CF3 is preferred, and -F is more preferred.

[0303] In the above general formula (5), at least one of X, Y and Z preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0304] In the general formula (5), Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond.

[0305] The number of carbon atoms of the fluorinated alkylene group is preferably 2 or more. In addition, the number of carbon atoms of the fluorinated alkylene group is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less. Examples of the fluorinated alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The fluorinated alkylene group is preferably a perfluoroalkylene group.

[0306] The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less.

[0307] As the fluorine-containing alkylene group having an ether bond, for example, the following formula is also preferred:

[0308] [Chemistry 4]

[0309]

[0310] (Where Z 1 F or CF3; Z 2 and Z 3 H or F; Z 4 is a divalent group represented by H, F or CF3; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0311] Specific examples of the fluorinated alkylene group having an ether bond include -CF(CF3)CF2-O-CF(CF3)-, -(CF(CF3)CF2-O) n -CF(CF3)- (wherein n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n -CF(CF3)CH2- (wherein n is an integer of 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0312] In the above general formula (5), Y 3 Preferably -COOM, -SO3M or -OSO3M (M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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).

[0313] As R 7 The organic group in is preferably an alkyl group. 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4The organic group is preferably H or C 1-4 of alkyl.

[0314] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0315] As the above-mentioned M, -H, a metal atom or -NR 7 4, more preferably -H, alkali metal (Group 1), alkaline earth metal (Group 2) or -NR 7 4, further preferably -H, -Na, -K, -Li or -NH4, still more preferably -Na, -K or -NH4, particularly preferably -Na or -NH4, and most preferably -NH4.

[0316] As the above Y 3 , preferably -COOM or -SO3M, more preferably -COOM.

[0317] The monomer represented by the general formula (5) is preferably a monomer (5b) represented by the following general formula (5b).

[0318] CH2=CF(-CF2-O-Rf-Y 3 )(5b)

[0319] (In the formula, Rf and Y 3 Same as above.)

[0320] Specific examples of the monomer represented by the general formula (5b) include the following:

[0321] [Chemistry 5]

[0322]

[0323] (Where Z 1 F or CF3; Z 2 and Z 3 H or F; Z 4 is H, F or CF3; p1+q1+r1 is an integer from 0 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5, Y 3 Same as above. Where Z 3 and Z 4 When all are H, p1+q1+r1+s1 is not 0). More specifically, preferably,

[0324] [Chemistry 6]

[0325]

[0326] CH2=CFCF2OCH2CF2-Y 3, CH2=CFCF2O(CH2CF2CF2O)CH2CF2-Y 3 ,

[0327] CH2=CFCF2OCH2CF2CH2-Y 3 ,

[0328] CH2=CFCF2O(CH2CF2CF2O)CH2CF2CH2-Y 3 ,

[0329] CH2=CFCF2OCF2CF2-Y 3 , CH2=CFCF2O(CF2CF2CF2O)CF2CF2-Y 3 ,

[0330] CH2=CFCF2OCF2CF2CH2-Y 3 ,

[0331] CH2=CFCF2O(CF2CF2CF2O)CF2CF2CH2-Y 3 ,

[0332] CH2=CFCF2OCF2-Y 3 , CH2=CFOF2O(CF2CF2O)CF2-Y 3 ,

[0333] CH2=CFCF2OCF2CH2-Y 3 ,

[0334] CH2=CFCF2O(CF2CF2O)CF2CH2-Y3,

[0335] etc., among which preferably

[0336] [Chemistry 7]

[0337]

[0338] As the monomer represented by the general formula (5b), Y in the general formula (5b) is preferably 3 It is -COOM, and particularly preferably at least one selected from the group consisting of CH2=CFCF20CF(CF3)COOM and CH2=CFCF20CF(CF3)CF20CF(CF3)COOM (wherein M has the same meaning as above).

[0339] The monomer represented by the general formula (5) is preferably a monomer (5c) represented by the following general formula (5c).

[0340] CX 2 2=CFCF2-O-(CF(CF3)CF2O)n5 -CF(CF3)-Y 3 (5c)

[0341] (In the formula, each X 2 The same, represents F or H. n5 represents 0 or an integer from 1 to 10, Y 3 Same as the above definition.)

[0342] In the above formula (5c), from the perspective of stability of the obtained aqueous dispersion, the above n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1. From the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 -COOM is preferred, and M is preferably H or NH 4 because it is less likely to remain as an impurity and the heat resistance of the obtained molded body is improved.

[0343] Examples of the monomer represented by the above formula (5c) include CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M has the same meaning as defined above).

[0344] Examples of the monomer represented by the general formula (5) include a monomer represented by the following general formula (5d).

[0345] CF2=CFCF2-O-Rf-Y 3 (5d)

[0346] (In the formula, Rf and Y 3 Same as above)

[0347] More specifically, we can cite

[0348] [Chemistry 8]

[0349] CF2=CFCF2OCF2CF2CF2-Y 3 ,

[0350]

[0351] CF2=CFCF2OCF2CF2CF2CH2-Y 3 ,

[0352] wait.

[0353] In the above general formula (6), X is -H or -F. Both 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.

[0354] In the above general formula (6), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group.

[0355] The alkyl group is an alkyl group not containing fluorine atoms and may have at least 1 carbon atom. The alkyl group may have preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms, and even more preferably 3 or less carbon atoms.

[0356] The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and the number of carbon atoms may be 1 or more. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0357] As the above-mentioned Y, -H, -F or -CF3 is preferred, and -F is more preferred.

[0358] In the above general formula (6), Y 3 Preferably -COOM, -SO3M or -OSO3M (M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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).

[0359] As R 7 The organic group in is preferably an alkyl group. 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is preferably H or C 1-4 of alkyl.

[0360] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0361] As the above-mentioned M, -H, a metal atom or -NR 7 4, more preferably -H, alkali metal (Group 1), alkaline earth metal (Group 2) or -NR 7 4, further preferably -H, -Na, -K, -Li or -NH4, still more preferably -Na, -K or -NH4, particularly preferably -Na or -NH4, and most preferably -NH4.

[0362] As the above Y 3 , preferably -COOM or -SO3M, more preferably -COOM.

[0363] In the above general formula (6), at least one of X and Y preferably contains a fluorine atom. For example, X may be -H, and Y and Z may be -F.

[0364] In the general formula (6), Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond.

[0365] The number of carbon atoms of the fluorinated alkylene group is preferably 2 or more. In addition, the number of carbon atoms of the fluorinated alkylene group is preferably 30 or less, more preferably 20 or less, and further preferably 10 or less. Examples of the fluorinated alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The fluorinated alkylene group is preferably a perfluoroalkylene group.

[0366] The monomer represented by the general formula (6) is preferably at least one selected from the group consisting of monomers represented by the following general formulae (6a) to (6f).

[0367] CF2=CF-O-(CF2) n1 -Y 3 (6a)

[0368] (where n1 represents an integer from 1 to 10, Y 3 Same as the above definition.)

[0369] CF2=CF-O-(CF2C(CF3)F) n2 -Y 3 (6b)

[0370] (where n2 represents an integer from 1 to 5, Y 3 Same as the above definition.)

[0371] CF2=CF-O-(CFX 1 ) n3 -Y 3 (6c)

[0372] (Where X 1 represents F or CF3, n3 represents an integer from 1 to 10, Y 3 Same as the above definition.)

[0373] CF2=CF-O-(CF2CFX 1 O) n4 -CF2CF2-Y 3 (6d)

[0374] (where n4 represents an integer from 1 to 10, Y 3 and X 1 Same as the above definition.)

[0375] CF2=CF-O-(CF2CF2CFX1 O) n5 -CF2CF2CF2-Y 3 (6e)

[0376] (where n5 represents an integer from 1 to 10, Y 3 and X 1 Same as the above definition.)

[0377] CF2=CF-O(-CF2) n6 -O-CF2-Y 3 (6f)

[0378] (where n6 represents an integer from 1 to 6, Y 3 and X 1 Same as the above definition.)

[0379] 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. From the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 -COOM is preferred, and M is preferably H or NH 4 because it is less likely to remain as an impurity and the heat resistance of the obtained molded body is improved.

[0380] Examples of the monomer represented by the above formula (6a) include CF2=CF-O-CF2COOM, CF2=CF(OCF2CF2COOM) and CF2=CF(OCF2CF2CF2COOM) (wherein M has the same meaning as defined above).

[0381] In the above formula (6b), from the perspective of the stability of the obtained aqueous dispersion, the above n2 is preferably an integer of 3 or less, and from the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, Y 3 -COOM is preferred, and M is preferably H or NH 4 because it is less likely to remain as an impurity and the heat resistance of the obtained molded body is improved.

[0382] In the above formula (6c), from the viewpoint of water solubility, the above n3 is preferably an integer of 5 or less, and from the viewpoint of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 It is preferably -COOM, and from the viewpoint of improving dispersion stability, the above-mentioned M is preferably H or NH4.

[0383] In the above formula (6d), from the perspective of the stability of the aqueous dispersion, the above X 1 Preferably -CF3, from the perspective of water solubility, the above n4 is preferably an integer of 5 or less, from the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3It is preferably -COOM, and the above-mentioned M is preferably H or NH4.

[0384] Examples of the monomer represented by the above formula (6d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2COOM, and CF2=CFOCF2CF(CF3)OCF2CF2CF2OOM (wherein M represents H, NH4 or an alkali metal).

[0385] In the general formula (6e), from the viewpoint of water solubility, the above n5 is preferably an integer of 5 or less, and from the viewpoint of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 It is preferably -COOM, and the above-mentioned M is preferably H or NH4.

[0386] Examples of the monomer represented by the general formula (6e) include CF2=CFOCF2CF2CF2COOM (wherein M represents H, NH4 or an alkali metal).

[0387] Examples of the compound represented by the general formula (6f) include CF2=CFOCF2CF2CF2OCF2COOM (wherein M represents H, NH4 or an alkali metal).

[0388] 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), at least one of X and Y preferably contains a fluorine atom.

[0389] The monomer represented by the general formula (7) is preferably selected from the following general formula (7a):

[0390] CF2=CF-(CF2) n1 -Y 3 (7a)

[0391] (where n1 represents an integer from 1 to 10, Y 3 The monomers represented by (a) and (b) are the same as those defined above, and the following general formula (7b):

[0392] CF2=CF-(CF2C(CF3)F) n2 -Y 3 (7b)

[0393] (where n2 represents an integer from 1 to 5, Y 3 At least one of the group consisting of monomers represented by (same as defined above).

[0394] The above Y 3 Preferably -SO3M or -COOM, M is preferably H, metal atom, NR 74. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 7 represents H or an organic group.

[0395] 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. From the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, the above Y 3 -COOM is preferred, and M is preferably H or NH 4 because it is less likely to remain as an impurity and the heat resistance of the obtained molded body is improved.

[0396] Examples of the monomer represented by the above formula (7a) include CF2=CFCF2COOM (wherein M has the same meaning as defined above).

[0397] In the above formula (7b), from the perspective of the stability of the obtained aqueous dispersion, the above n2 is preferably an integer of 3 or less, and from the perspective of obtaining appropriate water solubility and stability of the aqueous dispersion, Y 3 -COOM is preferred, and M is preferably H or NH 4 because it is less likely to remain as an impurity and the heat resistance of the obtained molded body is improved.

[0398] As the above-mentioned fluorine-containing compound (A), it is preferred that at least one selected from the group consisting of a monomer represented by the general formula (5), a monomer represented by the general formula (6) and a monomer represented by the general formula (7), more preferably at least one selected from the group consisting of a monomer represented by the general formula (5) and a monomer represented by the general formula (6), and further preferably a monomer represented by the general formula (5).

[0399] In addition, as the monomer represented by the general formula (5), it is preferred that at least one selected from the group consisting of the monomer represented by the general formula (5b), the monomer represented by the general formula (5c) and the monomer represented by the general formula (5d). Among them, it is more preferred that at least one selected from the group consisting of the monomer represented by the general formula (5b) and the monomer represented by the general formula (5c), and the monomer represented by the general formula (5b) is further preferred.

[0400] As the hydrocarbon-based surfactant (B), for example, hydrocarbon-based surfactants described in JP-A-2013-542308, JP-A-2013-542309, and JP-A-2013-542310 can be used.

[0401] The hydrocarbon surfactant (B) may be a surfactant having a hydrophilic group and a hydrophobic group in the same molecule, and may be cationic, nonionic or anionic.

[0402] Cationic hydrocarbon surfactants generally have a positively charged hydrophilic group such as an alkylated ammonium halide such as an alkylated ammonium bromide and a hydrophobic group such as a long-chain fatty acid.

[0403] Anionic hydrocarbon-based surfactants generally have a hydrophilic group such as a carboxylate, a sulfonate, or a sulfate, and a hydrophobic group such as an alkyl group as a long-chain hydrocarbon portion.

[0404] The nonionic hydrocarbon surfactant generally does not contain a charged group, but has a hydrophobic group which is a long-chain hydrocarbon. The hydrophilic group of the nonionic hydrocarbon surfactant contains a water-soluble functional group such as a vinyl ether chain derived from polymerization with ethylene oxide.

[0405] Examples of nonionic hydrocarbon surfactants

[0406] Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerides, and derivatives thereof.

[0407] Specific examples of the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like.

[0408] Specific examples of polyoxyethylene alkylphenyl ether include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and the like.

[0409] Specific examples of polyoxyethylene alkyl esters include polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, and the like.

[0410] Specific examples of sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like.

[0411] Specific examples of polyoxyethylene sorbitan alkyl esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and the like.

[0412] Specific examples of glycerides include glyceryl monotetradecanoate, glyceryl monostearate, glyceryl monooleate, and the like.

[0413] Specific examples of the above derivatives include polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

[0414] The above ethers and esters may have an HLB value of 10-18.

[0415] Examples of the nonionic hydrocarbon surfactant include Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol (registered trademark) L series, Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4 (m to 22, n to 23) and Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10) manufactured by BASF, and the like.

[0416] Examples of the anionic hydrocarbon-based surfactant include Versatic (registered trademark) 10 manufactured by Resolution Performance Products and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

[0417] The hydrocarbon surfactant (B) is preferably a compound containing anionic and / or nonionic hydrophilic groups, and more preferably a compound containing anionic hydrophilic groups. The hydrocarbon surfactant (B) may contain, for example, only anionic hydrophilic groups, only nonionic hydrophilic groups, or both anionic and nonionic hydrophilic groups.

[0418] In addition, as the above-mentioned hydrocarbon-based surfactant (B), only compounds containing anionic hydrophilic groups may be used, only compounds containing nonionic hydrophilic groups may be used, or a compound containing anionic hydrophilic groups and a compound containing nonionic hydrophilic groups may be used in combination.

[0419] The hydrocarbon-based surfactant (B) preferably does not contain a functional group capable of reacting in radical polymerization.

[0420] As the hydrocarbon surfactant, there can also be mentioned RLM (wherein, R is a linear or branched alkyl group having 1 or more carbon atoms which may be substituted or not, or a cyclic alkyl group having 3 or more carbon atoms which may be substituted or not, and when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. L is -ArSO3 - 、-SO3 - 、-SO4-、-PO3 - or -COO - , M is H, metal atom, NR 54. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5 H or an organic group, -ArSO3 - is an anionic surfactant represented by aryl sulfonate. 5 It is preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms.

[0421] Specifically, lauric acid, lauryl sulfate (dodecyl sulfate), and the like are representative examples of CH3-(CH2) n -LM (wherein n is an integer of 6 to 17. L and M are the same as described above).

[0422] A mixture of substances in which R is an alkyl group having 12 to 16 carbon atoms and LM is a sulfate may also be used.

[0423] Examples of hydrocarbon surfactants include: 6 (-LM)2(where R 6 It is a linear or branched alkylene group having 1 or more carbon atoms which may be substituted or a cyclic alkylene group having 3 or more carbon atoms which may be substituted or not. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. L is -ArSO3 - 、-SO3 - 、-SO4-、-PO3 - or -COO - , M is H, metal atom, NR 5 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5 H or an organic group, -ArSO3 - Anionic surfactant represented by aryl sulfonate).

[0424] Examples of the hydrocarbon surfactant include: 7 (-LM)3(where R 7 It is a linear or branched alkylene group having 1 or more carbon atoms which may be substituted, or a cyclic alkylene group having 3 or more carbon atoms which may be substituted. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. L is -ArSO3 - 、-SO3 - 、-SO4 - 、-PO3 - or -COO - , M is H, metal atom, NR5 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5 H or an organic group. -ArSO3 - Anionic surfactant represented by aryl sulfonate).

[0425] As R 5 , preferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, further preferably H or an alkyl group having 1 to 4 carbon atoms.

[0426] In this specification, unless otherwise stated, "substituent" means a group that can be substituted. Examples of such "substituent" include: aliphatic group, aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, 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 an aliphatic amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thiol group, an aromatic thiol group, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group or a diaromatic oxyphosphinyl group.

[0427] As the above-mentioned hydrocarbon surfactant (B), siloxane hydrocarbon surfactants can also be mentioned. As siloxane hydrocarbon surfactants, substances described in Silicone Surfactants, RMHill, Marcel Dekker, Inc., ISBN: 0-8247-00104 can be mentioned. The structure of siloxane hydrocarbon surfactants contains clear hydrophobic groups and hydrophilic groups. The hydrophobic group contains more than one dihydrocarbyl siloxane unit, where the substituents on the silicon atom are all hydrocarbons.

[0428] When the carbon atoms of the hydrocarbon group may be substituted by halogen such as fluorine, these siloxane hydrocarbon-based surfactants may also be regarded as hydrocarbon-based surfactants in the sense that they are completely substituted by hydrogen atoms, that is, the monovalent substituent on the carbon atom of the hydrocarbon group is hydrogen.

[0429] The hydrophilic group of the siloxane surfactant may include one or more polar parts containing ionic groups such as sulfate, sulfonate, phosphonate, phosphate, carboxylate, carbonate, sulfosuccinate, taurate (in the form of free acid, salt or ester), phosphine oxide, betaine, betaine polyol, quaternary ammonium salt, etc. The ionic hydrophobic group may also include ionic functionalized siloxane grafts. As such siloxane surfactants, for example, polydimethylsiloxane-grafted-(meth)acrylate, polydimethylsiloxane-grafted-polyacrylate salt and polydimethylsiloxane grafted quaternary amine can be cited.

[0430] The polar portion of the hydrophilic group of the silicone surfactant may include polyethers such as polyoxyethylene (PEO) and mixed polyoxyethylene / oxypropylene polyethers (PEO / PPO); monosaccharides and disaccharides; and nonionic groups formed from water-soluble heterocycles such as pyrrolidone. The ratio of ethylene oxide to propylene oxide (EO / PO) may vary in the mixed polyoxyethylene / oxypropylene polyethers.

[0431] The hydrophilic group of the siloxane surfactant may also include a combination of an ionic part and a nonionic part. Such a part may include, for example, an ionic end-functionalized or randomly functionalized polyether or polyol. In the practice of the present invention, siloxanes having a nonionic part, i.e., nonionic siloxane surfactants, are preferred.

[0432] The configuration of the hydrophobic and hydrophilic groups of the structure of the siloxane surfactant can take the form of a diblock polymer (AB), a triblock polymer (ABA) (where "B" represents the siloxane portion of the molecule), or a multiblock polymer. Alternatively, the siloxane surfactant can include a grafted polymer.

[0433] Silicone hydrocarbon-based surfactants are also disclosed in US Pat. No. 6,841,616.

[0434] Examples of the silicone-based anionic hydrocarbon surfactant include Noveon (registered trademark) from Lubrizol Advanced Materials, Inc., SilSense available from Consumer Specialties, and TM PE-100Silicone、SilSense TM CA-1Silicone, etc.

[0435] Examples of the anionic hydrocarbon-based surfactant include sulfosuccinate surfactant Lankropol (registered trademark) K8300 manufactured by Akzo Nobel Surface Chemistry LLC.

[0436] Examples of the sulfosuccinate surfactant include diisodecyl sulfosuccinate sodium salt (Emulsogen (registered trademark) SB10 from Clariant), diisotridecyl sulfosuccinate sodium salt (Polirol (registered trademark) TR / LNA from Cesapinia Chemicals), and the like.

[0437] Examples of the hydrocarbon-based surfactant include PolyFox (registered trademark) surfactants from Omnova Solutions, Inc. TM PF-156A, PolyFox TM PF-136A, etc.).

[0438] As the hydrocarbon-based surfactant, an anionic hydrocarbon-based surfactant is preferable. As the anionic hydrocarbon-based surfactant, the above-mentioned ones can be used, and for example, the following hydrocarbon-based surfactants can be preferably used.

[0439] Examples of the hydrocarbon-based surfactant include hydrocarbon-based surfactants having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group).

[0440] As the hydrocarbon surfactant having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), the preferred formula is: R x -X(where R x It is a non-fluorinated organic group having 1 to 2000 carbon atoms and having one or more carbonyl groups (excluding the carbonyl group in the carboxyl group), and X is -OSO3X 1 、-COOX 1 or -SO3X 1 (X 1 H, metal atoms, NR 1x 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 1x R is H or an organic group, which may be the same or different)) as shown in the surfactant. x The number of carbon atoms is preferably 500 or less, more preferably 100 or less, further preferably 50 or less, and still more preferably 30 or less.

[0441] As the hydrocarbon-based surfactant, it is more preferably selected from the following formula (a):

[0442] [Chemistry 9]

[0443]

[0444] (Where R1a It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, the hydrogen atoms bonded to the carbon atoms may be substituted by a hydroxyl group or a monovalent organic group containing an ester bond, when the number of carbon atoms is 2 or more, it may contain a carbonyl group, when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. 2a and R 3a R is independently a single bond or a divalent linking group. 1a , R 2a and R 3a The total number of carbon atoms in X is 6 or more. a H, metal atoms, NR 4a 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 4a R is H or an organic group and may be the same or different. 1a , R 2a and R 3a Any two of them can be bonded to each other to form a ring) represented by the surfactant (a), the following formula (b):

[0445] [Chemistry 10]

[0446]

[0447] (Where R 1b It is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring. 2b and R 4b R is independently H or a substituent. 3b is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer greater than 1. p and q are independently an integer greater than 0. b H, metal atoms, NR 5b 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5b R is H or an organic group and may be the same or different. 1b , R 2b , R 3b and R 4b Any two of them can be bonded to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6bCO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6 CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6b It is H or an alkyl group with 1 to 4 carbon atoms which may have a substituent. * refers to -OSO3X in the formula b The surfactant (b) shown on the bonding side, and the following formula (c):

[0448] [Chemistry 11]

[0449]

[0450] (Where R 1c It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group or a monovalent organic group containing an ester bond, when the number of carbon atoms is 2 or more, it may contain a carbonyl group, when the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring, or may form a ring. 2c and R 3c R is independently a single bond or a divalent linking group. 1c , R 2c and R 3c The total number of carbon atoms in A is 5 or more. c For-COOX c or -SO3X c (X c H, metal atoms, NR 4c 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 4c is H or an organic group, which may be the same or different). 1c , R 2c and R 3c Any two of them can be bonded to each other to form a ring) and the following formula (d):

[0451] [Chemistry 12]

[0452]

[0453] (Where R 1d It is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. When the group has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring. 2dand R 4d R is independently H or a substituent. 3d A is an alkylene group having 1 to 10 carbon atoms which may have a substituent. n is an integer greater than 1. p and q are independently an integer greater than 0. d SO3X d or -COOX d (X d H, metal atoms, NR 5d 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5d is H or an organic group, which may be the same or different). 1d , R 2d , R 3d and R 4d Any two of them can be bonded to form a ring. L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6d is H or an alkyl group having 1 to 4 carbon atoms which may or may not have a substituent. * refers to the d At least one of the group consisting of the surfactants (d) shown on the bonding side).

[0454] The surfactant (a) is described.

[0455] In formula (a), R 1a It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0456] When the number of carbon atoms of the above-mentioned alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be included between two carbon atoms. In addition, when the number of carbon atoms of the above-mentioned alkyl group is 2 or more, the above-mentioned carbonyl group may be included at the end of the above-mentioned alkyl group. That is, acyl groups such as acetyl groups represented by CH3-C(=O)- are also included in the above-mentioned alkyl group.

[0457] In addition, when the number of carbon atoms of the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, and more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include a furan ring and the like. 1aIn the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0458] It should be noted that, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocyclic ring. For example, the number of carbon atoms of the group represented by CH3-C(=O)-CH2- is 3, the number of carbon atoms of the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- is 7, and the number of carbon atoms of the group represented by CH3-C(=O)- is 2.

[0459] In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0460] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 101a (Where R 101a is an alkyl group.

[0461] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably the alkyl group is non-halogenated and does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0462] In the formula, R 2a and R 3a are independently a single bond or a divalent linking group.

[0463] R 2a and R 3a Preferably, each of them is independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0464] Composition R 2a and R 3a The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0465] In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0466] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 102a (Where R 102a is an alkyl group.

[0467] In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0468] R 1a , R 2a and R 3a The total number of carbon atoms is 6 or more. The total number of carbon atoms is preferably 8 or more, more preferably 9 or more, and further preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, and further preferably 15 or less.

[0469] R 1a , R 2a and R 3a Any two of them can be bonded to each other to form a ring.

[0470] In formula (a), X a H, metal atoms, NR 4a 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 4a H or an organic group. 4 R 4a They may be the same or different. 4a , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, including alkali metals (Group 1) and alkaline earth metals (Group 2), preferably Na, K or Li. a , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 4a 4, H, Na, K, Li or NH4 is more preferred due to its easy solubility in water, Na, K or NH4 is further preferred due to its even greater solubility in water, Na or NH4 is particularly preferred, and NH4 is most preferred due to its easy removal. a When NH 4 is used, the above surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the fluorine-containing elastomer or the final product.

[0471] As R 1a , preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a straight-chain or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms and containing a monovalent or divalent heterocycle.

[0472] In addition, as R1a , more preferably the following formula:

[0473] [Chemistry 13]

[0474]

[0475] (where n 11a is an integer from 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, R 12a It is an alkylene group having 0 to 3 carbon atoms. 11a When R is an integer of 2 to 10, 12a The groups shown in (a) and (b) may be the same or different.

[0476] As n 11a , preferably an integer of 0-5, more preferably an integer of 0-3, further preferably an integer of 1-3.

[0477] As R 11a The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0478] As R 11a In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0479] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 103a (Where R 103a is an alkyl group.

[0480] As R 11a In the above-mentioned alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0481] R 12a It is an alkylene group having 0 to 3 carbon atoms. The above-mentioned carbon number is preferably 1 to 3.

[0482] As R 12a The above-mentioned alkylene group may be linear or branched.

[0483] As R 12a The above alkylene group preferably does not contain a carbonyl group. 12a , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0484] As R12a In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0485] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 104a (Where R 104a is an alkyl group.

[0486] As R 12a In the above-mentioned alkylene group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0487] As R 2a and R 3a , preferably independently an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0488] Next, the surfactant (b) will be described.

[0489] In formula (b), R 1b It 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.

[0490] When the number of carbon atoms of the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, and more preferably an oxygen-containing unsaturated heterocyclic ring, for example, a furan ring. 1b In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0491] It should be noted that, in the present specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the above-mentioned heterocyclic ring.

[0492] About R 1b The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

[0493] As R 1b The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0494] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably the alkyl group is non-halogenated and does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0495] The above-mentioned alkyl group preferably has no substituent.

[0496] As R 1b , preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a substituent, still more preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms without a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0497] In formula (b), R 2b and R 4b are independently H or a substituent. 2b and R 4b They may be the same or different, respectively.

[0498] About R 2b and R 4b The substituent is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

[0499] As R 2b and R 4b The above alkyl group preferably does not contain a carbonyl group. In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0500] The above-mentioned alkyl group preferably has no substituent.

[0501] About R 2b and R 4bThe above-mentioned alkyl group is preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group with 3 to 10 carbon atoms which does not contain a carbonyl group, more preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms which does not contain a carbonyl group, further preferably a straight-chain or branched alkyl group with 1 to 3 carbon atoms which does not have a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0502] As R 2b and R 4b , preferably independently H or a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group, more preferably H or a linear or branched alkyl group having 1 to 3 carbon atoms not having a substituent, further more preferably H, methyl (-CH3) or ethyl (-C2H5), and particularly preferably H.

[0503] In formula (b), R 3b R is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3b When there are two or more, they may be the same or different.

[0504] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0505] In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0506] The above-mentioned alkylene group preferably has no substituent.

[0507] As the above-mentioned alkylene group, preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted or a cyclic alkylene group having 3 to 10 carbon atoms which may be substituted or not, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group, further preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0508] R 1b , R 2b , R 3b and R 4b Any two of them may be bonded to each other to form a ring, but preferably do not form a ring.

[0509] In formula (b), n is an integer greater than or equal to 1. As n, an integer of 1 to 40 is preferred, an integer of 1 to 30 is more preferred, an integer of 5 to 25 is further preferred, and an integer of 5 to 9 or 11 to 25 is particularly preferred.

[0510] In formula (b), p and q are independently an integer greater than or equal to 0. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0511] The total of n, p and q is preferably an integer of 5 or more. The total of n, p and q is more preferably an integer of 8 or more. The total of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and further preferably an integer of 40 or less.

[0512] In formula (b), X b H, metal atoms, NR 5b 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5b H or an organic group. 4 R 5b They may be the same or different. 5b , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, including alkali metals (Group 1) and alkaline earth metals (Group 2), preferably Na, K or Li. X b It can be a metal atom or NR 5b 4(R 5b as described above).

[0513] As X b , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 5b 4, H, Na, K, Li or NH4 is more preferred due to its easy solubility in water, Na, K or NH4 is further preferred due to its even greater solubility in water, Na or NH4 is particularly preferred, and NH4 is most preferred due to its easy removal. b When NH 4 is used, the above surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the fluorine-containing elastomer or the final product.

[0514] In formula (b), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6b -B-*, -NR 6b CO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6b -B-, -NR 6CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6b is H or an alkyl group having 1 to 4 carbon atoms which may be substituted. The alkylene group more preferably has 1 to 5 carbon atoms. 6 More preferably, it is H or methyl. * refers to -OSO3X in the formula b Bonding side.

[0515] L is preferably a single bond.

[0516] As the surfactant (b), the following formula is preferred:

[0517] [Chemistry 14]

[0518]

[0519] (Where R 1b , R 2b , L, n and X b As described above).

[0520] The above surfactant (b) 1 The integrated value of all peak intensities observed in the chemical shift region of 2.0 ppm to 5.0 ppm in the H-NMR spectrum is preferably 10% or more.

[0521] The above surfactant (b) 1 The integrated value of all peak intensities observed in the chemical shift region of 2.0 ppm to 5.0 ppm in the H-NMR spectrum is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0522] In the surfactant (b), the integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and further preferably 70 or less.

[0523] The above integrated value was measured at room temperature using a deuterated water solvent, with the deuterated water content being 4.79 ppm.

[0524] The surfactant (c) is described.

[0525] In formula (c), R 1c It is a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

[0526] When the number of carbon atoms of the above-mentioned alkyl group is 3 or more, a carbonyl group (-C(=O)-) may be contained between two carbon atoms. In addition, when the number of carbon atoms of the above-mentioned alkyl group is 2 or more, the above-mentioned carbonyl group may be contained at the end of the above-mentioned alkyl group. That is, acyl groups such as acetyl groups represented by CH3-C(=O)- are also contained in the above-mentioned alkyl group.

[0527] In addition, when the number of carbon atoms of the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, and more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include a furan ring and the like. 1c In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0528] It should be noted that, in this specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the above-mentioned heterocyclic ring. For example, the number of carbon atoms of the group represented by CH3-C(=O)-CH2- is 3, the number of carbon atoms of the group represented by CH3-C(=O)-C2H4-C(=O)-C2H4- is 7, and the number of carbon atoms of the group represented by CH3-C(=O)- is 2.

[0529] In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0530] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 101c (Where R 101c is an alkyl group.

[0531] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably the alkyl group is non-halogenated and does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0532] In formula (c), R 2c and R 3c are independently a single bond or a divalent linking group.

[0533] R 2c and R 3c Each of the groups is independently a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

[0534] Composition R 2c and R 3cThe above-mentioned alkylene group preferably does not contain a carbonyl group.

[0535] In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (—OH) or a monovalent organic group containing an ester bond, but is preferably not substituted with any functional group.

[0536] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 102c (Where R 102c is an alkyl group.

[0537] In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but a non-halogenated alkylene group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0538] R 1c , R 2c and R 3c The total number of carbon atoms is 5 or more. The total number of carbon atoms is preferably 7 or more, more preferably 9 or more, and is preferably 20 or less, more preferably 18 or less, and further preferably 15 or less.

[0539] R 1c , R 2c and R 3c Any two of them can be bonded to each other to form a ring.

[0540] In formula (c), A c For-COOX c or -SO3X c (X c H, metal atoms, NR 4c 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 4c is H or an organic group, which may be the same or different). 4c , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, including alkali metals (Group 1) and alkaline earth metals (Group 2), preferably Na, K or Li.

[0541] As X c , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 4c4, H, Na, K, Li or NH4 is more preferred due to its easy solubility in water, Na, K or NH4 is further preferred due to its even greater solubility in water, Na or NH4 is particularly preferred, and NH4 is most preferred due to its easy removal. c When NH 4 is used, the above surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the fluorine-containing elastomer or the final product.

[0542] As R 1c , preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a straight-chain or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or an alkyl group having 3 to 45 carbon atoms and containing a monovalent or divalent heterocycle.

[0543] In addition, as R 1c , more preferably the following formula:

[0544] [Chemistry 15]

[0545]

[0546] (where n 11c is an integer from 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, R 12c It is an alkylene group having 0 to 3 carbon atoms. 11c When R is an integer of 2 to 10, 12c The groups shown in (a) and (b) may be the same or different.

[0547] As n 11c , preferably an integer of 0-5, more preferably an integer of 0-3, further preferably an integer of 1-3.

[0548] As R 11c The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0549] As R 11c In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0550] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 103c (Where R 103c is an alkyl group.

[0551] As R11c In the above-mentioned alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0552] R 12c It is an alkylene group having 0 to 3 carbon atoms. The above-mentioned carbon number is preferably 1 to 3.

[0553] As R 12c The above-mentioned alkylene group may be linear or branched.

[0554] As R 12c The above alkylene group preferably does not contain a carbonyl group. 12c , more preferably ethylene (-C2H4-) or propylene (-C3H6-).

[0555] As R 12c In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted by a functional group, for example, by a hydroxyl group (-OH) or a monovalent organic group containing an ester bond, but is preferably not substituted by any functional group.

[0556] Examples of the monovalent organic group containing an ester bond include a group of the formula: -OC(=O)-R 104c (Where R 104c is an alkyl group.

[0557] As R 12c In the above-mentioned alkylene group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0558] As R 2c and R 3c , preferably independently an alkylene group having 1 or more carbon atoms and not containing a carbonyl group, more preferably an alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group, and further preferably an ethylene group (-C2H4-) or a propylene group (-C3H6-).

[0559] The surfactant (d) is described.

[0560] In formula (d), R 1d It 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.

[0561] When the number of carbon atoms of the alkyl group is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, and more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include a furan ring and the like. 1d In the above, the divalent heterocyclic ring may be inserted between two carbon atoms, the divalent heterocyclic ring may be located at the terminal and bonded to -C(=O)-, and the monovalent heterocyclic ring may be located at the terminal of the above alkyl group.

[0562] It should be noted that, in the present specification, the "number of carbon atoms" of the above-mentioned alkyl group also includes the number of carbon atoms constituting the above-mentioned heterocyclic ring.

[0563] About R 1d The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

[0564] As R 1d The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0565] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably the alkyl group is non-halogenated and does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0566] The above-mentioned alkyl group preferably has no substituent.

[0567] As R 1d , preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a substituent, still more preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms without a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0568] In formula (d), R 2d and R 4d are independently H or a substituent. 2d and R 4d They may be the same or different, respectively.

[0569] About R 2d and R 4dThe substituent is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

[0570] As R 2d and R 4d The above alkyl group preferably does not contain a carbonyl group. In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, and less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0571] The above-mentioned alkyl group preferably has no substituent.

[0572] About R 2d and R 4d The above-mentioned alkyl group is preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group with 3 to 10 carbon atoms which does not contain a carbonyl group, more preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms which does not contain a carbonyl group, further preferably a straight-chain or branched alkyl group with 1 to 3 carbon atoms which does not have a substituent, and particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5).

[0573] As R 2d and R 4d , preferably independently H or a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group, more preferably H or a linear or branched alkyl group having 1 to 3 carbon atoms not having a substituent, further more preferably H, methyl (-CH3) or ethyl (-C2H5), and particularly preferably H.

[0574] In formula (d), R 3d R is an alkylene group having 1 to 10 carbon atoms which may have a substituent. 3d When there are two or more, they may be the same or different.

[0575] The above-mentioned alkylene group preferably does not contain a carbonyl group.

[0576] In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, 50% or less may be substituted by halogen atoms, or 25% or less may be substituted by halogen atoms, but a non-halogenated alkyl group containing no halogen atoms such as fluorine atoms and chlorine atoms is preferred.

[0577] The above-mentioned alkylene group preferably has no substituent.

[0578] As the above-mentioned alkylene group, preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted or a cyclic alkylene group having 3 to 10 carbon atoms which may be substituted or not, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms which does not contain a carbonyl group, further preferably a linear or branched alkylene group having 1 to 10 carbon atoms which does not contain a substituent, and still more preferably a methylene group (-CH2-), an ethylene group (-C2H4-), an isopropylene group (-CH(CH3)CH2-) or a propylene group (-C3H6-).

[0579] R 1d , R 2d , R 3d and R 4d Any two of them can be bonded to each other to form a ring.

[0580] In formula (d), n is an integer of 1 or more. As n, an integer of 1-40 is preferable, an integer of 1-30 is more preferable, and an integer of 5-25 is further preferable.

[0581] In formula (d), p and q are independently an integer greater than or equal to 0. p is preferably an integer of 0 to 10, more preferably 0 or 1. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

[0582] The total of n, p and q is preferably an integer of 6 or more. The total of n, p and q is more preferably an integer of 8 or more. The total 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.

[0583] In formula (d), A d SO3X d or -COOX d (X d H, metal atoms, NR 5d 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 5d is H or an organic group, which may be the same or different). 5d , preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms. Examples of the metal atom include monovalent and divalent metal atoms, including alkali metals (Group 1) and alkaline earth metals (Group 2), preferably Na, K or Li. X d It can be a metal atom or NR 5d 4(R 5d as described above).

[0584] As Xd , preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 5d 4, H, Na, K, Li or NH4 is more preferred due to its easy solubility in water, Na, K or NH4 is further preferred due to its even greater solubility in water, Na or NH4 is particularly preferred, and NH4 is most preferred due to its easy removal. d When NH 4 is used, the above surfactant has excellent solubility in an aqueous medium and metal components are less likely to remain in the fluorine-containing elastomer or the final product.

[0585] In formula (d), L is a single bond, -CO2-B-*, -OCO-B-*, -CONR 6d -B-*, -NR 6d CO-B-*, or -CO- (excluding -CO2-B-, -OCO-B-, -CONR 6d -B-, -NR 6d CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms which may be substituted, R 6d is H or an alkyl group having 1 to 4 carbon atoms which may be substituted. The alkylene group more preferably has 1 to 5 carbon atoms. 6d More preferably, it is H or methyl. * refers to d Bonding side.

[0586] L is preferably a single bond.

[0587] The above surfactants 1 The integrated value of all peak intensities observed in the chemical shift region of 2.0 ppm to 5.0 ppm in the H-NMR spectrum is preferably 10 or more.

[0588] The above surfactants 1 The integrated value of all peak intensities observed in the chemical shift region of 2.0 ppm to 5.0 ppm in the H-NMR spectrum is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

[0589] In the above-mentioned surfactants, the above-mentioned integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and further preferably 70 or less.

[0590] The above integrated value was measured at room temperature using a deuterated water solvent, with the deuterated water content being 4.79 ppm.

[0591] As surfactants (a) to (d), surfactants described in International Publication Nos. 2018 / 062448, 2018 / 062449, 2018 / 18906, and 2018 / 18907 can be used, and for example, CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3X b (X b As described above), CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2A d (A d as described above) etc.

[0592] Examples of the anionic hydrocarbon-based surfactant include the following formula (α):

[0593] R 10 -COOM(α)

[0594] (Where R 10 is a monovalent organic group containing one or more carbon atoms. M is H, a metal atom, NR 11 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 11 is H or an organic group, which may be the same or different) as shown in the surfactant (α). 11 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 of organic groups.

[0595] From the perspective of surface activity, R 10 The number of carbon atoms in is preferably 2 or more, more preferably 3 or more. In addition, from the perspective of water solubility, R 10 The number of carbon atoms is preferably 29 or less, more preferably 23 or less.

[0596] Examples of the metal atom of M include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K, or Li is preferred. M is preferably H, a metal atom, or NR 11 4, more preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 11 4, further preferably H, Na, K, Li or NH4, still more preferably Na, K or NH4, particularly preferably Na or NH4, and most preferably NH4.

[0597] Examples of the surfactant (α) include: 12 -COOM (where R 12It is a linear or branched alkyl, alkenyl, alkylene or alkenylene group with or without a substituent having 1 or more carbon atoms, or a cyclic alkyl, alkenyl, alkylene or alkenylene group with or without a substituent having 3 or more carbon atoms, which may also contain an ether bond. When the number of carbon atoms is 3 or more, it may contain a monovalent or divalent heterocyclic ring or form a ring. M is the same as above) represented by an anionic surfactant. Specifically, CH3-(CH2) n -COOM (wherein n is an integer of 2 to 28 and M is the same as described above).

[0598] From the viewpoint of emulsification stability, the surfactant (α) may not contain a carbonyl group (excluding the carbonyl group in the carboxyl group).

[0599] As the hydrocarbon-containing surfactant not containing a carbonyl group, for example, the following formula (α-1) can be preferably exemplified:

[0600] R 13 -COO-M(α-1)

[0601] (Where R 13 is an alkyl, alkenyl, alkylene or alkenylene group, which may contain an ether bond. M is H, a metal atom, NR 11 4. An imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent. 11 The same or different compounds are H or an organic group having 1 to 10 carbon atoms.

[0602] In the above formula (α-1), R 13 Preferably, it is an alkyl group or an alkenyl group (which may contain an ether group). 13 The alkyl or alkenyl group in may be linear or branched. 13 The number of carbon atoms in is not limited, but is, for example, 2 to 29, preferably 4 to 29.

[0603] R 13 The number of carbon atoms in the alkyl group may be 6 to 17. 13 The number of carbon atoms in is preferably 3 to 29, more preferably 5 to 23. When the above alkyl group is branched, R 13 The number of carbon atoms in the moiety is preferably 5-35, more preferably 11-23.

[0604] When the alkenyl group is linear, the number of carbon atoms in R is preferably 2 to 29, more preferably 9 to 23. When the alkenyl group is branched, the number of carbon atoms in R is preferably 4 to 29, more preferably 9 to 23.

[0605] Examples of the alkyl group and alkenyl group include a methyl group, an ethyl group, an isobutyl group, a tert-butyl group, and a vinyl group.

[0606] As R 10 , R 12 , R 13 , preferably a hydrocarbon group, more preferably a hydrocarbon group containing no unsaturated bond, further preferably a linear or branched alkyl group, particularly preferably a linear alkyl group.

[0607] R 10 , R 12 , R 13 The hydrocarbon group of R may be a group consisting of only carbon atoms and hydrogen atoms. 10 , R 12 , R 13 , may be a hydrocarbon group not containing a carbonyl group, or may be an alkyl group not containing a carbonyl group.

[0608] As R 10 , R 12 , R 13 The number of carbon atoms in the hydrocarbon group is preferably 1 to 2,000, more preferably 1 to 30, further preferably 5 to 24, particularly preferably 8 to 18.

[0609] As R 10 , R 12 , R 13 The number of carbon atoms in the alkyl group is preferably 1-2,000, more preferably 1-30, further preferably 5-24, particularly preferably 8-18.

[0610] Examples of the surfactant (α) (carboxylic acid-type hydrocarbon surfactant) include butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)-linolenic acid, eleostearic acid, arachidic acid, 8,11-eicosadienoic acid, eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, Palmitoleic acid, cis-6-hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, α-eleostearic acid, β-eleostearic acid, eicosatrienoic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, octadecatetraenoic acid, arachidonic acid, eicosatetraenoic acid, docosatetraenoic acid, octadecateneic acid, eicosapentaenoic acid, docosapentaenoic acid, sardine acid, tetracospentaenoic acid, docosahexaenoic acid, herring acid, and salts thereof.

[0611] In particular, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof is preferred.

[0612] Examples of the salt include a salt in which the hydrogen of the carboxyl group is a metal atom of the above formula M, NR 11 4. Salts of imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, are not particularly limited.

[0613] As the above-mentioned surfactant (α) (carboxylic acid type hydrocarbon surfactant), since fluorine-containing elastomer particles with a small average particle size can be obtained by polymerization, and a large amount of fluorine-containing elastomer particles are generated during polymerization, the fluorine-containing elastomer can be effectively manufactured. Therefore, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid and their salts is preferred, lauric acid and its salts are further preferred, lauric acid salts are particularly preferred, and sodium laurate is most preferred.

[0614] As the hydrocarbon-based surfactant, preferably, the following general formula (β) can be exemplified:

[0615] [Chemistry 16]

[0616]

[0617] (Where R 1 ~R 5 represents H or a monovalent substituent, wherein R 1 and R 3 At least one of them represents the general formula: -YR 6 The group shown, R 2 and R 5 At least one of the following represents a group represented by the general formula: -XA or a group represented by the general formula: -YR 6 The groups shown.

[0618] In addition, X is the same or different at each occurrence and is a divalent linking group or a bonding bond;

[0619] A is the same or different at each occurrence and represents -COOM, -SO3M or -OSO3M (M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group);

[0620] Y is the same or different at each occurrence and represents a group consisting of -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 -and-NR 8A divalent connecting group or bond in the group consisting of CO-, R 8 is H or an organic group;

[0621] R 6 The same or different groups at each occurrence represent 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 between carbon atoms.

[0622] R 1 ~R 5 Any two of them may be bonded to each other to form a ring) (hereinafter also referred to as surfactant (β)).

[0623] The surfactant (β) is described.

[0624] In the formula, R 1 ~R 5 represents H or a monovalent substituent, wherein R 1 and R 3 At least one of them represents the general formula: -YR 6 The group shown, R 2 and R 5 At least one of the following represents a group represented by the general formula: -XA or a group represented by the general formula: -YR 6 The group shown. 1 ~R 5 Any two of them can be bonded to each other to form a ring.

[0625] As R 1 The substituent that the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

[0626] As R 1 The above-mentioned alkyl group preferably does not contain a carbonyl group.

[0627] In the above alkyl group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably the alkyl group is non-halogenated and does not contain halogen atoms such as fluorine atoms and chlorine atoms.

[0628] The above-mentioned alkyl group preferably has no substituent.

[0629] As R 1, preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms with or without a substituent, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms without a carbonyl group, further preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms without a substituent, still more preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms without a substituent, particularly preferably a methyl group (-CH3) or an ethyl group (-C2H5), and most preferably a methyl group (-CH3).

[0630] As a monovalent substituent, preferably a general formula: -YR 6 The group shown in the general formula: -XA, -H, C with or without a substituent 1-20 Alkyl, -NH2, -NHR 9 (R 9 is an organic group), -OH, -COOR 9 (R 9 is an organic group) or -OR 9 (R 9 The alkyl group preferably has 1 to 10 carbon atoms.

[0631] As R 9 , preferably C 1-10 Alkyl or C 1-10 Alkylcarbonyl, more preferably C 1-4 Alkyl or C 1-4 of an alkylcarbonyl group.

[0632] In the formula, X is the same or different each time it appears, and represents a divalent linking group or a bonding bond. 6 When any of a carbonyl group, an ester group, an amide group, and a sulfonyl group is not included, X is preferably a divalent linking group including at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group.

[0633] As X, it is preferred to include a compound selected from the group consisting of -CO-, -S(=O)2-, -O-, -COO-, -OCO-, -S(=O)2-O-, -OS(=O)2-, -CONR 8 -and-NR 8 A divalent connecting group having at least one bond in the group consisting of CO-, C 1-10 An alkylene group or a bond. 8 represents H or an organic group.

[0634] As R 8 , preferably H or C 1-10 An organic group, more preferably H or C 1-4The organic group is more preferably H.

[0635] In the formula, A is the same or different at each occurrence, representing -COOM, -SO3M or -OSO3M (M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 H or an organic group. 4 R 7 In the general formula (β), one preferred embodiment is that A is -COOM.

[0636] As R 7 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 of organic groups.

[0637] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li is preferred.

[0638] As M, H, a metal atom or NR 7 4, more preferably H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4, further preferably H, Na, K, Li or NH4, still more preferably Na, K or NH4, particularly preferably Na or NH4, and most preferably NH4.

[0639] In the formula, Y is the same or different at each occurrence and represents a compound selected from -S(=O)2-, -O-, -COO-, -OCO-, -CONR 8 -and-NR 8 A divalent connecting group or bond in the group consisting of CO-, R 8 represents H or an organic group.

[0640] As Y, it is preferable to be selected from the group consisting of a bonding bond, -O-, -COO-, -OCO-, -CONR 8 -and-NR 8 The divalent linking group selected from the group consisting of -CO- is more preferably a divalent linking group selected from the group consisting of a bonding bond, -COO- and -OCO-.

[0641] As R 8 , preferably H or C 1-10 An organic group, more preferably H or C 1-4 The organic group is more preferably H.

[0642] In the formula, R 6is the same or different at each occurrence, and indicates an alkyl group having 1 or more carbon atoms that may or may not contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group, and a sulfonyl group between carbon atoms. 6 The number of carbon atoms in the organic group is preferably 2 or more and 20 or less, more preferably 2-20, and even more preferably 2-10.

[0643] R 6 When the number of carbon atoms of the alkyl group is 2 or more, it may contain one or more carbonyl groups, ester groups, amide groups and sulfonyl groups between carbon atoms, but these groups are not contained at both ends of the alkyl group. 6 In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0644] As R 6 , preferably

[0645] General formula: -R 10 -CO-R 11 The groups shown,

[0646] General formula: -R 10 -COO-R 11 The groups shown,

[0647] General formula: -R 11 The groups shown,

[0648] General formula: -R 10 -NR 8 CO-R 11 The group shown, or

[0649] General formula: -R 10 -CONR 8 -R 11 The groups shown,

[0650] (Where R 8 Represents H or an organic group. 10 is an alkylene group, R 11 is an alkyl group which may have a substituent).

[0651] As R 6 , more preferably the general formula: -R 10 -CO-R 11 The groups shown.

[0652] As R 8 , preferably H or C 1-10An organic group, more preferably H or C 1-4 The organic group is more preferably H.

[0653] R 10 The number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. 10 The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 3 to 10 carbon atoms.

[0654] R 11 The number of carbon atoms in the alkyl group may be 1 to 20, preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10, still further preferably 1 to 8, particularly further preferably 1 to 6, further further preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1. 11 The alkyl group of R is preferably composed of only primary carbon, secondary carbon, and tertiary carbon, and is particularly preferably composed of only primary carbon and secondary carbon. 11 , preferably methyl, ethyl, n-propyl, isopropyl, and most preferably methyl.

[0655] In the general formula (β), R 2 and R 5 It is also a preferred embodiment that at least one of them is a group represented by the general formula: -XA, and the A is -COOM.

[0656] As the surfactant (β), preferred are compounds represented by the general formula (β-1), compounds represented by the general formula (β-2) or compounds represented by the general formula (β-3), and more preferred are compounds represented by the general formula (β-1) or compounds represented by the general formula (β-2).

[0657] General formula (β-1):

[0658] [Chemistry 17]

[0659]

[0660] (Where R 3 ~R 6 , X, A and Y are as described above. )

[0661] General formula (β-2):

[0662] [Chemistry 18]

[0663]

[0664] (Where R 4 ~R 6 , X, A and Y are as described above. ) General formula (β-3):

[0665] [Chemistry 19]

[0666]

[0667] (Where R 2 , R 4 ~R 6 , X, A and Y are as described above. ) As the group represented by the general formula: -XA, preferably -COOM,

[0668] -R 12 COOM,

[0669] -SO3M,

[0670] -OSO3M,

[0671] -R 12 SO3M,

[0672] -R 12 OSO3M,

[0673] -OCO-R 12 -COOM,

[0674] -OCO-R 12 -SO3M,

[0675] -OCO-R 12 -OSO3M

[0676] -COO-R 12 -COOM,

[0677] -COO-R 12 -SO3M,

[0678] -COO-R 12 -OSO3M,

[0679] -CONR 8 -R 12 -COOM,

[0680] -CONR 8 -R 12 -SO3M,

[0681] -CONR 8 -R 12 -OSO3M,

[0682] -NR 8 CO-R 12 -COOM,

[0683] -NR 8 CO-R 12 -SO3M,

[0684] -NR 8 CO-R 12 -OSO3M,

[0685] -OS(=O)2-R 12 -COOM,

[0686] -OS(=O)2-R 12 -SO3M, or

[0687] -OS(=O)2-R 12 -OSO3M

[0688] (Where R 8 and M as above. R 12 C 1-10 of alkylene. ).

[0689] The above R 12 In the alkylene group, less than 75% of hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkylene group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0690] As general formula: -YR 6 The groups shown are preferably

[0691] General formula: -R 10 -CO-R 11 The groups shown,

[0692] General formula: -OCO-R 10 -CO-R 11 The groups shown,

[0693] General formula: -COO-R 10 -CO-R 11 The groups shown,

[0694] General formula: -OCO-R 10 -COO-R 11 The groups shown,

[0695] General formula: -COO-R 11 The groups shown,

[0696] General formula: -NR 8 CO-R 10 -CO-R 11 The group shown, or

[0697] General formula: -CONR 8 -R 10 -NR8 CO-R 11 The groups shown

[0698] (Where R 8 , R 10 and R 11 as described above).

[0699] In the formula, as R 4 and R 5 , independently preferably H or C 1-4 of alkyl.

[0700] The above R 4 and R 5 In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0701] As R in the general formula (β-1) 3 , preferably H or C with or without substituents 1-20 alkyl, more preferably H or unsubstituted C 1-20 The alkyl group is more preferably H.

[0702] The above R 3 In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0703] As R in the general formula (β-3) 2 , preferably H, OH or C with or without substitution 1-20 alkyl, more preferably H, OH or unsubstituted C 1-20 The alkyl group is more preferably H or OH.

[0704] The above R 2 In the alkyl group, less than 75% of the hydrogen atoms bonded to the carbon atoms may be substituted by halogen atoms, less than 50% may be substituted by halogen atoms, or less than 25% may be substituted by halogen atoms, but preferably it is a non-halogenated alkyl group not containing halogen atoms such as fluorine atoms and chlorine atoms.

[0705] As the hydrocarbon surfactant (B), an anionic hydrocarbon surfactant is preferred, and particularly preferred are -PO3M (-PO(OM)2), -OPO3M (-OPO(OM)2), -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2 (M is H, metal atom, NR 74. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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). More preferably, it is a hydrocarbon surfactant having -SO3M, -OSO3M or -COOM (M is the same as above). When two M are contained in each formula, the two M may be the same or different.

[0706] Examples of the anionic hydrocarbon-based surfactant include the following general formula (γ):

[0707] R 14 -Y 3 (γ)

[0708] (Where R 14 represents an aliphatic hydrocarbon group which may contain a carbonyl group. 3 Is a hydrophilic group. ) is a surfactant (γ) shown.

[0709] Y in the above general formula (γ) 3 Preferably -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2 (in each formula, M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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).

[0710] R 14 The aliphatic hydrocarbon group preferably has 1 to 2,000 carbon atoms, more preferably 1 to 100 carbon atoms, further preferably 1 to 30 carbon atoms, particularly preferably 5 to 24 carbon atoms, and most preferably 8 to 18 carbon atoms.

[0711] In the above general formula (γ), R 14 An aliphatic hydrocarbon group containing one or more carbonyl groups is preferred. Examples of such a surfactant include the above-mentioned surfactant (a) and surfactant (b).

[0712] In the above general formula (γ), R 14 The aliphatic hydrocarbon group is also preferably a straight-chain or branched alkyl group. The carbon number of the alkyl group is preferably 1 to 2000, more preferably 1 to 30, further preferably 5 to 24, and particularly preferably 8 to 18. Examples of such surfactants include CH3-(CH2) n -OSO3M (wherein n is an integer of 7 to 17 and M is the same as above).

[0713] The hydrocarbon-based surfactant (B) is preferably at least one selected from the group consisting of the surfactant (c), surfactant (d), surfactant (α), surfactant (β) and surfactant (γ).

[0714] Another example of a surfactant suitable as the hydrocarbon-based surfactant (B) is a general formula:

[0715] R 15 -Y 5

[0716] (Where R 15 is an aliphatic hydrocarbon group, Y 5 is a hydrophilic group) shown as a surfactant.

[0717] As R 15 The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group containing no unsaturated bond, more preferably a linear or branched alkyl group, and further preferably a linear alkyl group.

[0718] R 15 The aliphatic hydrocarbon group may be a group consisting of only carbon atoms and hydrogen atoms. 15 , may be an aliphatic hydrocarbon group not containing a carbonyl group, or may be an aliphatic hydrocarbon group not containing a carbonyl group.

[0719] As R 15 The number of carbon atoms in the hydrocarbon group is preferably 1 to 2,000, more preferably 1 to 30, further preferably 5 to 24, particularly preferably 8 to 18.

[0720] Another example of a surfactant suitable as the hydrocarbon-based surfactant (B) is a general formula:

[0721] CH3-(CH2) n -Y 5

[0722] (where n is an integer from 1 to 2000, Y 5 is a hydrophilic group) shown as a surfactant.

[0723] As Y 5 , preferably -NH2, -PO3M (-PO(OM)2), -OPO3M (-OPO(OM)2), -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2 (in each formula, M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7is 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), more preferably -PO3M (-PO(OM)2), -OPO3M (-OPO(OM)2), -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2, further preferably -SO3M, -OSO3M or -COOM.

[0724] As a component of Y 5 The M is preferably H, an alkali metal or NH4, more preferably H, Na, K or NH4.

[0725] As the hydrocarbon surfactant (B), at least one selected from the group consisting of heptanoic acid, heptylsulfonic acid, heptylsulfuric acid, octanoic acid, octylsulfonic acid, octylsulfuric acid, nonanoic acid, nonylsulfonic acid, nonylsulfuric acid, decanoic acid, decylsulfonic acid, decylsulfuric acid, undecylenic acid, undecylsulfonic acid, undecylsulfuric acid, lauric acid, dodecylsulfonic acid, dodecylsulfuric acid (laurylsulfuric acid), tridecanoic acid, tridecylsulfonic acid, tridecylsulfuric acid and salts thereof is preferred, and at least one selected from the group consisting of laurylsulfuric acid, octylsulfuric acid, lauric acid, dodecylsulfonic acid and salts thereof is more preferred. As the salts thereof, sodium salts, potassium salts and ammonium salts thereof are preferred.

[0726] In the production method of the present invention, two or more of the above-mentioned hydrocarbon-based surfactants may be used simultaneously.

[0727] In the production method of the present invention, the emulsion polymerization can be carried out by, for example, adding pure water and the fluorine-containing compound (A) and the hydrocarbon surfactant (B) into a pressure-resistant reaction vessel equipped with a stirrer, adding monomers after deoxygenation, making it reach a predetermined temperature, adding a polymerization initiator, and initiating the reaction. Since the pressure decreases as the reaction proceeds, in order to maintain the initial pressure, additional monomers are continuously or intermittently supplied, and the supply is stopped at the moment when a predetermined amount of monomers is supplied, and the monomers in the reaction vessel are purged to return the temperature to room temperature, thereby terminating the reaction.

[0728] In the above-mentioned emulsion polymerization, the amount of the fluorinated compound (A) is preferably an amount equivalent to 3ppm to 5000ppm of the aqueous medium. The amount of the fluorinated compound (A) is preferably an amount equivalent to 5ppm or more of the aqueous medium, more preferably an amount equivalent to 10ppm or more, further preferably an amount equivalent to 20ppm or more, particularly preferably an amount equivalent to 30ppm or more, and more preferably an amount equivalent to 1000ppm or less, an amount equivalent to 500ppm or less, further preferably an amount equivalent to 85ppm or less, and particularly preferably an amount equivalent to 75ppm or less.

[0729] It is also preferred to adjust the amount of the fluorine-containing compound (A) by the type of the polymerization initiator used in the polymerization and the polymerization temperature.

[0730] When a non-redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at 40°C to 70°C, the amount of the fluorinated compound (A) is preferably an amount equivalent to 3ppm to 300ppm of the aqueous medium, more preferably an amount equivalent to 3ppm to 150ppm, further preferably an amount equivalent to 5ppm to 100ppm, and most preferably an amount equivalent to 8ppm to 80ppm.

[0731] When a non-redox polymerization initiator is used as a polymerization initiator and the polymerization is carried out at a temperature above 70°C and below 98°C, the amount of the fluorinated compound (A) is preferably an amount equivalent to 3ppm to 500ppm of the aqueous medium, more preferably an amount equivalent to 3ppm to 200ppm, further preferably an amount equivalent to 5ppm to 120ppm, and most preferably an amount equivalent to 20ppm to 110ppm.

[0732] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at a temperature above 10°C and below 40°C, the amount of the fluorinated compound (A) is preferably an amount equivalent to 3ppm to 300ppm of the aqueous medium, more preferably an amount equivalent to 3ppm to 100ppm, further preferably an amount equivalent to 5ppm to 80ppm, and most preferably an amount equivalent to 10ppm to 70ppm.

[0733] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at 40°C to 70°C, the amount of the fluorinated compound (A) is preferably an amount equivalent to 3ppm to 500ppm of the aqueous medium, more preferably an amount equivalent to 5ppm to 300ppm, further preferably an amount equivalent to 10ppm to 200ppm, and most preferably an amount equivalent to 15ppm to 150ppm.

[0734] When a redox polymerization initiator is used as a polymerization initiator and the polymerization is carried out at a temperature above 70°C and below 98°C, the amount of the fluorinated compound (A) is preferably an amount equivalent to 5ppm to 500ppm of the aqueous medium, more preferably an amount equivalent to 8ppm to 300ppm, further preferably an amount equivalent to 15ppm to 200ppm, and most preferably an amount equivalent to 20ppm to 150ppm.

[0735] By setting it as the said range, the adhesion rate can be further reduced, and the polymerization time can be shortened.

[0736] The fluorine-containing compound (A) is preferably added before the polymerization initiator is added to initiate the polymerization reaction. Alternatively, it is preferably added only before initiating the polymerization reaction and not added after the initiation of the polymerization.

[0737] In the above-mentioned emulsion polymerization, the amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 3ppm to 5000ppm of the aqueous medium. The amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 5ppm or more of the aqueous medium, more preferably an amount equivalent to 10ppm or more, further preferably an amount equivalent to 20ppm or more, and particularly preferably an amount equivalent to 30ppm or more, and more preferably an amount equivalent to 1000ppm or less, further preferably an amount equivalent to 500ppm or less, and particularly preferably an amount equivalent to 200ppm or less.

[0738] It is also preferred to adjust the amount of the hydrocarbon-based surfactant (B) by the type of the polymerization initiator used in the polymerization and the polymerization temperature.

[0739] When a non-redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at 40°C to 70°C, the amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 5ppm to 500ppm of the aqueous medium, more preferably an amount equivalent to 5ppm to 300ppm, further preferably an amount equivalent to 10ppm to 200ppm, and most preferably an amount equivalent to 25ppm to 120ppm.

[0740] When a non-redox polymerization initiator is used as a polymerization initiator and the polymerization is carried out at a temperature exceeding 70°C and below 98°C, the amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 3ppm to 300ppm of the aqueous medium, more preferably an amount equivalent to 3ppm to 250ppm, further preferably an amount equivalent to 5ppm to 100ppm, and most preferably an amount equivalent to 10ppm to 70ppm.

[0741] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at a temperature above 10°C and below 40°C, the amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 3 ppm to 500 ppm of the aqueous medium, more preferably an amount equivalent to 5 ppm to 350 ppm, further preferably an amount equivalent to 10 ppm to 250 ppm, and most preferably an amount equivalent to 25 ppm to 210 ppm.

[0742] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at 40°C to 70°C, the amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 3ppm to 500ppm of the aqueous medium, more preferably an amount equivalent to 5ppm to 350ppm, further preferably an amount equivalent to 10ppm to 250ppm, and most preferably an amount equivalent to 20ppm to 200ppm.

[0743] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at a temperature exceeding 70°C and below 98°C, the amount of the hydrocarbon surfactant (B) is preferably an amount equivalent to 5ppm to 500ppm of the aqueous medium, more preferably an amount equivalent to 10ppm to 300ppm, further preferably an amount equivalent to 15ppm to 200ppm, and most preferably an amount equivalent to 25ppm to 100ppm.

[0744] By setting it as the said range, it is possible to further reduce the adhesion rate and shorten the polymerization time.

[0745] The hydrocarbon-based surfactant (B) is preferably added before the polymerization initiator is added to initiate the polymerization reaction. Alternatively, it is preferably added only before initiating the polymerization reaction and not added after the initiation of the polymerization.

[0746] In the emulsion polymerization, the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, further preferably 15 / 85 to 65 / 35, particularly preferably 20 / 80 to 60 / 40.

[0747] By setting it as the said range, it is possible to further reduce the adhesion rate and shorten the polymerization time.

[0748] It is also preferred to adjust the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) by the type of the polymerization initiator used in the polymerization and the polymerization temperature.

[0749] When a non-redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 40°C to 70°C, the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) is preferably 7 / 93 to 80 / 20, more preferably 10 / 90 to 65 / 35, and further preferably 15 / 85 to 40 / 60.

[0750] When a non-redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at a temperature exceeding 70°C and below 98°C, the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) is preferably 15 / 85 to 85 / 15, more preferably 20 / 80 to 80 / 20, and still more preferably 30 / 70 to 60 / 40.

[0751] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at a temperature of 10°C or higher and lower than 40°C, the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) is preferably 5 / 95 to 70 / 30, more preferably 10 / 90 to 60 / 40, and still more preferably 15 / 85 to 35 / 65.

[0752] When a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 40°C to 70°C, the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) is preferably 5 / 95 to 70 / 30, more preferably 10 / 90 to 60 / 40, and further preferably 15 / 85 to 50 / 50.

[0753] When a redox polymerization initiator is used as a polymerization initiator and polymerization is carried out at a temperature exceeding 70° C. and below 98° C., the mass ratio (A / B) of the fluorinated compound (A) to the hydrocarbon surfactant (B) is preferably 5 / 95 to 70 / 30, more preferably 10 / 90 to 60 / 40, and still more preferably 15 / 85 to 50 / 50.

[0754] The emulsion polymerization is preferably carried out in the presence of a polymerization initiator such as a free radical polymerization initiator. The free radical polymerization initiator is not particularly limited as long as it can generate free radicals in the above polymerization temperature range, and a known oil-soluble and / or water-soluble polymerization initiator can be used, but a water-soluble polymerization initiator is preferred.

[0755] Furthermore, the polymerization may be initiated as a redox initiator in combination with a reducing agent, etc. The concentration of the polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the target fluorine-containing elastomer, and the reaction rate.

[0756] The concentration of the polymerization initiator added is appropriately determined depending on the molecular weight of the target fluorinated elastomer and the polymerization reaction rate, and is set to 0.0001 to 10 mass %, preferably 0.01 to 5 mass %, based on 100 mass % of the total monomer amount.

[0757] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0758] The oil-soluble free radical polymerization initiator may be a known oil-soluble peroxide, and for example, the following peroxides may be cited as representative substances: dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate; dialkyl peroxides such as di-tert-butyl peroxide; and di(ω-hydro-dodecafluorohexanoyl) peroxide, di(ω-hydro-tetradecafluoroheptanoyl) peroxide, di(ω-hydro-hexadecanoyl) peroxide, di(ω-hydro-hexadecanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluoropentanoyl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(perfluorooctanoyl) peroxide. peroxide, di(perfluorononanoyl)peroxide, di(ω-chloro-hexafluorobutyryl)peroxide, di(ω-chloro-decafluorohexanoyl)peroxide, di(ω-chloro-tetrafluorooctanoyl)peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexafluorononanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydro-dodecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutyryl)peroxide, di(trichlorooctafluorohexanoyl)peroxide, di(tetrachloroundecanoyl)peroxide, di(pentachlorotetrafluorodecanoyl)peroxide, di(undecanotridodecanoyl)peroxide and the like di[perfluoro(or fluorochloro)acyl]peroxides; and the like.

[0759] As the water-soluble free radical polymerization initiator, it can be a known water-soluble peroxide, for example, ammonium salts, potassium salts, sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonic acid, etc., organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide, tert-butyl peroxymaleate, tert-butyl hydroperoxide, etc. It can also contain a reducing agent such as sulfites and sulfites, and its amount can be 0.1 to 20 times that of the peroxide.

[0760] As the water-soluble peroxide, salts of persulfate are preferred because the amount of generated free radicals can be easily adjusted, and potassium persulfate (K2S2O8) and ammonium persulfate ((NH4)2S2O8) are preferred, with ammonium persulfate being most preferred.

[0761] When the polymerization is carried out using a water-soluble peroxide at a polymerization temperature of 45° C. or higher, it is preferred that the polymerization be carried out without using a reducing agent.

[0762] For example, when the polymerization is carried out at a low temperature of 60° C. or lower, a redox initiator combining an oxidizing agent and a reducing agent is preferably used as the polymerization initiator. That is, the emulsion polymerization is preferably carried out in the presence of a redox initiator.

[0763] As the above-mentioned oxidizing agent, persulfate, organic peroxide, potassium permanganate, manganese triacetate, ammonium cerium nitrate, bromate, etc. can be mentioned. As the reducing agent, sulfite, bisulfite, bromate, diimine, oxalic acid, sulfinic acid metal salt, etc. can be mentioned. As persulfate, ammonium persulfate and potassium persulfate can be mentioned. As sulfite, sodium sulfite and ammonium sulfite can be mentioned. In order to increase the decomposition rate of the initiator, it is also preferred to add copper salts and iron salts to the combination of redox initiators. As copper salts, copper sulfate (II) can be mentioned, and as iron salts, iron sulfate (II) can be mentioned. In addition, when copper salts and iron salts are used, it is particularly preferred to add a chelating agent. As a chelating agent, disodium ethylenediaminetetraacetic acid dihydrate is preferred.

[0764] Examples of the redox initiator include potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / iron (II) sulfate, ammonium persulfate / sulfite / iron (II) sulfate, ammonium persulfate / sulfite, ammonium persulfate / iron (II) sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / sulfite, bromate / bisulfite, ammonium persulfate / sodium hydroxymethanesulfinate dihydrate, and the like, preferably ammonium persulfate / sodium hydroxymethanesulfinate dihydrate.

[0765] When a redox initiator is used, either the oxidant or the reductant may be placed in a polymerization tank in advance, and then the other may be added continuously or intermittently to initiate polymerization. For example, when ammonium persulfate / sodium hydroxymethanesulfinate dihydrate is used, it is preferred that ammonium persulfate be placed in the polymerization tank and sodium hydroxymethanesulfinate dihydrate be added continuously thereto.

[0766] The amount of the persulfate in the redox initiator used is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.5% by mass, and particularly preferably 0.05 to 1.0% by mass, based on the aqueous medium used in the emulsion polymerization.

[0767] The amount of the reducing agent used is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, and particularly preferably 5% by mass to 20% by mass, based on the aqueous medium used in the emulsion polymerization.

[0768] The amount of the third component (copper salt, iron salt, etc.) used is preferably 0.001 to 0.5 mass %, more preferably 0.005 to 0.4 mass %, and particularly preferably 0.01 to 0.3 mass % relative to the aqueous medium used in the emulsion polymerization.

[0769] One of the preferred embodiments is to carry out the emulsion polymerization in the presence of a water-soluble polymerization initiator, a fluorine-containing compound (A) and a hydrocarbon surfactant (B).

[0770] Water-soluble polymerization initiators are distinguished from oil-soluble polymerization initiators such as oil-soluble peroxides. As water-soluble polymerization initiators, the above-mentioned water-soluble free radical polymerization initiators such as the above-mentioned salts of persulfate can be cited. In addition, redox initiators using water-soluble oxidizing agents and reducing agents are also water-soluble polymerization initiators. For example, as water-soluble polymerization initiators, redox initiators in which the oxidizing agent is persulfate, potassium permanganate, manganese triacetate, ammonium cerium nitrate or bromate, and the reducing agent is sulfite, bisulfite, bromate, diimide, oxalic acid or sulfinic acid metal salt can be cited.

[0771] It should be noted that in the above-mentioned method, as long as there is a period during which the water-soluble polymerization initiator, the fluorinated compound (A) and the hydrocarbon-based surfactant (B) are present simultaneously during the polymerization, it is not necessary for the water-soluble polymerization initiator, the fluorinated compound (A) and the hydrocarbon-based surfactant (B) to be present simultaneously during the entire polymerization period.

[0772] In the production method of the present invention, it is preferred that the fluorinated compound (A) is present in the aqueous medium before all polymerization initiators used in the polymerization step of emulsion polymerization to obtain the fluorinated elastomer are present. In addition, it is also preferred that the hydrocarbon surfactant (B) is present in the aqueous medium before all polymerization initiators used in the polymerization step of emulsion polymerization to obtain the fluorinated elastomer are present.

[0773] In the production method of the present invention, it is preferred that the fluorinated compound (A) and the hydrocarbon surfactant (B) are present before all polymerization initiators used in the polymerization step of obtaining the fluorinated elastomer by emulsion polymerization are present.

[0774] The above-mentioned "the total amount of polymerization initiators used in the polymerization step for obtaining the fluorinated elastomer" means the total amount of polymerization initiators added before the completion of the polymerization.

[0775] In addition, "before adding all the polymerization initiators" means, in polymerization, before adding the polymerization initiator added initially. For example, when adding the polymerization initiator 5 times, it means before the first addition. In addition, when the polymerization is performed separately as in seed polymerization, it means before adding the polymerization initiator used in the polymerization for producing seed particles.

[0776] It should be noted that, as a method for making the above-mentioned polymerization initiator exist, for example, a method of adding the polymerization initiator in a reaction vessel can be cited. In addition, as a method for making the above-mentioned fluorinated compound (A) or hydrocarbon surfactant (B) exist in an aqueous medium, for example, it can be put into a reaction vessel together with an aqueous medium, and it can also be added to the reaction vessel after putting into an aqueous medium. The same is true below.

[0777] In the polymerization step, the hydrocarbon surfactant (B) is preferably present in the aqueous medium when the solid content concentration of the fluorinated elastomer in the aqueous medium is 1.0 mass % or less. The hydrocarbon surfactant (B) is more preferably present when the solid content concentration is 0.8 mass % or less, further preferably when it is 0.5 mass % or less, still more preferably when it is 0.1 mass % or less, and particularly preferably when it is 0.0 mass %. The solid content concentration is the concentration of the solid content relative to the total of the aqueous medium and the fluorinated elastomer.

[0778] The hydrocarbon-based surfactant (B) may be present at the above-mentioned solid content concentration, and may or may not be added after exceeding the above-mentioned solid content concentration.

[0779] In the polymerization step, the hydrocarbon surfactant (B) is preferably present in the aqueous medium before the polymerization initiator is present. The hydrocarbon surfactant (B) may or may not be added after the polymerization initiator is present.

[0780] The polymerization step preferably allows the fluorinated compound (A) to be present in the aqueous medium when the solid content concentration of the fluorinated elastomer in the aqueous medium is 1.0% by mass or less. The fluorinated compound (A) is more preferably present when the solid content concentration is 0.8% by mass or less, further preferably when it is 0.5% by mass or less, still more preferably when it is 0.1% by mass or less, and particularly preferably when it is 0.0% by mass. The solid content concentration is the total concentration relative to the aqueous medium and the fluorinated elastomer. The fluorinated compound (A) may or may not be added after the solid content concentration exceeds 1.0% by mass.

[0781] In the polymerization step, the fluorine-containing compound (A) is preferably placed in the aqueous medium before the polymerization initiator is placed in the aqueous medium. The fluorine-containing compound (A) may be added after the polymerization initiator is added, or may not be added.

[0782] The above-mentioned polymerization step preferably allows the above-mentioned fluorinated compound (A) and the above-mentioned hydrocarbon-based surfactant (B) to be present in the aqueous medium when the solid content concentration of the fluorinated elastomer in the aqueous medium is 1.0 mass % or less. The above-mentioned fluorinated compound (A) and the above-mentioned hydrocarbon-based surfactant (B) are more preferably present when the above-mentioned solid content concentration is 0.8 mass % or less, further preferably when they are present when they are 0.5 mass % or less, still more preferably when they are present when they are 0.1 mass % or less, and particularly preferably when they are 0.0 mass %. The above-mentioned solid content concentration is the concentration relative to the total of the aqueous medium and the fluorinated elastomer. The above-mentioned fluorinated compound (A) and the above-mentioned hydrocarbon-based surfactant (B) may or may not be added after the above-mentioned solid content concentration exceeds 1.0 mass %.

[0783] In the polymerization step, the fluorinated compound (A) and the hydrocarbon surfactant (B) are preferably present in the aqueous medium before the polymerization initiator is present in the aqueous medium. The fluorinated compound (A) and the hydrocarbon surfactant (B) may be added after the polymerization initiator is added, or may not be added.

[0784] The temperature of the emulsion polymerization is preferably 10°C to 120°C, more preferably 20°C to 100°C, because a fluorine-containing elastomer providing a molded article having excellent physical properties can be obtained.

[0785] The temperature of the emulsion polymerization is preferably 15°C to 60°C, more preferably 18°C ​​to 55°C, and even more preferably 20°C to 50°C, from the viewpoint of stability of the aqueous dispersion and reduction in adhesion rate.

[0786] The temperature of the emulsion polymerization is preferably 60 to 120°C, more preferably 60 to 100°C, and even more preferably 70 to 90°C, because the reaction rate of the emulsion polymerization is high and a fluorinated elastomer having excellent physical properties can be obtained.

[0787] The emulsion polymerization is usually carried out at a pressure of 0.5 MPaG to 10 MPaG, preferably 1 MPaG to 7 MPaG.

[0788] The emulsion polymerization may use a chain transfer agent during the polymerization. As the chain transfer agent, known substances may be used, such as hydrocarbons, esters, ethers, alcohols, ketones, halogen-containing compounds, carbonates, etc. Among them, isopentane, diethyl malonate and ethyl acetate are preferred from the aspect that the reaction rate is not easy to decrease, and diiodide compounds such as I(CF2)4I, I(CF2)6I, and ICH2I are preferred from the aspect that the polymer terminal can be iodinated and can be used as a reactive polymer.

[0789] The amount of the chain transfer agent used is preferably 0.5×10 -3 Mole %~5×10 -3 mol%, preferably 1.0×10 -3 Mole %~3.5×10 -3 Mol %.

[0790] As the chain transfer agent, a bromine compound or an iodine compound is particularly preferably used. Examples of the polymerization method using a bromine compound or an iodine compound include iodine transfer polymerization and bromine transfer polymerization.

[0791] Iodine compounds and bromine compounds are water-insoluble and difficult to emulsify. Therefore, emulsion polymerization is inherently limited and tends to require the use of a large amount of surfactant. The production method of the present invention can obtain a fluorine-containing elastomer even by polymerization using an iodine compound or a bromine compound, such as iodine transfer polymerization or bromine transfer polymerization.

[0792] The above-mentioned iodine transfer polymerization is the following method: since the dissociation energy of the carbon-iodine bond is low, it has free radical activity, and the chain transfer reaction participates in the free radical polymerization process, and the active free radical polymerization caused by the free radical chain reactivation mechanism caused by this is utilized. Regarding the reaction conditions, known conditions can be appropriately utilized, and there is no particular limitation. For example, the conditions described in "Collection of Polymer Papers, Vol.49, No.10, pp.765-783, October 1992" and Japanese Patent Publication No. 53-3495 can be appropriately adopted. Bromine compounds can be used instead of iodine compounds to carry out the same polymerization. In this specification, such polymerization is referred to as bromine transfer polymerization.

[0793] Among them, iodine transfer polymerization is preferred from the perspectives of polymerization reactivity, cross-linking reactivity, and the like.

[0794] Representative examples of the above-mentioned bromine compounds or iodine compounds include, for example, the general formula:

[0795] R 8 I x Br y

[0796] (where x and y are integers from 0 to 2 and satisfy 1≤x+y≤2, R 8 is a saturated or unsaturated fluorocarbon or chlorofluorocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, wherein R 8 By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer to function as a crosslinking point.

[0797] Examples of the bromine compound and the iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodoperfluoropropane-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodoperfluoropentane-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodethane, 1,3-diiodoperfluoropropane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, BrCF2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluoro-1-butene, 2-bromo-4-iodoperfluoro-1-butene, mono-iodine and mono-bromine substitutions of benzene, di-iodine and mono-bromine substitutions, and (2-iodoethyl) and (2-bromoethyl) substitutions, etc. These compounds can be used alone or in combination with each other.

[0798] Among these, compounds containing no bromine and only iodine are preferred from the viewpoints of polymerization reactivity, crosslinking reactivity, and availability, and 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, or 2-iodoperfluoropropane is preferably used.

[0799] The aqueous medium is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a non-fluorinated organic solvent such as alcohol, ether, or ketone and / or a fluorinated organic solvent having a boiling point of 40° C. or less.

[0800] In the polymerization of the fluorinated elastomer, as a pH adjuster, phosphate, sodium hydroxide, potassium hydroxide or the like can be preferably used.

[0801] The above-mentioned emulsion polymerization may not be carried out in the presence of fluorine-containing monomer polymerization seed particles, in other words, may be carried out in the absence of fluorine-containing monomer polymerization seed particles.

[0802] The above-mentioned "fluorinated monomer polymerization seed particles" are obtained by polymerizing the above-mentioned fluorinated monomer in an aqueous medium, and are present in the second polymerization in which the types or existence ratios of the components such as monomers, additives (such as emulsifiers, polymerization initiators, etc.) constituting the polymerization reaction system, reaction conditions, etc. are different. The above-mentioned fluorinated monomer polymerization seed particles act as so-called seed particles during the above-mentioned emulsion polymerization, and constitute the so-called seed polymerization including emulsion polymerization in the presence of the seed particles. The above-mentioned emulsion polymerization may not be subjected to such seed polymerization. That is, the manufacturing method of the present invention may include the following polymerization steps (which do not include seed polymerization): in the presence of a fluorinated compound (A) containing a functional group and a hydrophilic group capable of reacting in free radical polymerization and a hydrocarbon-based surfactant (B), emulsion polymerization of the fluorinated monomer is carried out in an aqueous medium to obtain a fluorinated elastomer.

[0803] The adhesion rate of the emulsion polymerization polymer (fluorinated elastomer) on the polymerization tank is preferably 8% by mass or less. It is more preferably 4% by mass or less, further preferably 2% by mass or less, and most preferably 1% by mass or less. The production method of the present invention can reduce the above adhesion rate by conducting emulsion polymerization in the presence of a fluorinated compound (A) and a hydrocarbon surfactant (B).

[0804] The attachment rate is the ratio of the mass of polymer deposits attached to the polymerization tank after the polymerization is completed to the total amount of polymer (fluoroelastomer) after the polymerization is completed (the attachment rate on the polymerization tank). The polymer deposits include: polymers attached to the inner wall of the polymerization tank or the stirring blades inside the polymerization tank after the aqueous dispersion is extracted from the polymerization tank after the polymerization is completed; and polymers that are freed from the aqueous dispersion by coagulation and float or precipitate. The mass of polymer deposits is the mass after the water contained in the polymer deposits is dried and removed at 120°C.

[0805] Adhesion rate (mass %) = mass of polymer deposits / mass of obtained polymer (including deposits) × 100

[0806] The mass of the obtained polymer = the mass of the aqueous dispersion × the solid content concentration of the aqueous dispersion (mass %) / 100 + the mass of the attached matter

[0807] In the production method of the present invention, an aqueous dispersion of a fluorinated elastomer is obtained. The production method of the present invention may be a method for producing an aqueous dispersion of a fluorinated elastomer. The solid content concentration of the obtained aqueous dispersion of the fluorinated elastomer at the time of completion of polymerization is preferably 10% to 50% by mass, more preferably 15% to 40% by mass, and further preferably 20% to 30% by mass.

[0808] The solid content concentration of the aqueous dispersion of the fluorinated elastomer can be determined by drying 1 g of the aqueous dispersion at 150°C for 60 minutes, measuring the mass of the heating residue, and calculating the ratio of the mass of the heating residue to the mass of the aqueous dispersion.

[0809] In the aqueous dispersion of the fluorinated elastomer obtained by the production method of the present invention, the average particle size of the fluorinated elastomer particles is preferably 10 nm to 800 nm, more preferably 80 nm to 700 nm, and further preferably 100 nm to 600 nm. The average particle size in the present invention is a cumulative average particle size, which can be measured by a dynamic light scattering method.

[0810] In the aqueous dispersion of the fluorinated elastomer obtained by the production method of the present invention, the number of particles of the fluorinated elastomer is preferably 1.0×10 12 The number of particles is more preferably 5.0×10 12 / cc or more, more preferably 1.0×10 13 More than pcs / cc.

[0811] The above-mentioned number of particles (the number of polymer particles) is calculated according to the following formula.

[0812] [Number 1]

[0813]

[0814] The number of fluorine-containing elastomer particles obtained by the above formula is the number per 1 cc of water. The specific gravity is the specific gravity of the fluorine-containing elastomer.

[0815] The specific gravity of the fluorinated elastomer is determined in accordance with JIS Z 8807:2012.

[0816] The aqueous dispersion of the fluorinated elastomer obtained by the production process of the present invention is treated by precipitation, heating, etc. Each treatment is performed as follows.

[0817] The above-mentioned precipitation is carried out by adding alkaline earth and earth metal salts. Examples of the above-mentioned alkaline earth and earth metal salts include sulfates, nitrates, hydrochlorides and acetates of calcium, magnesium or aluminum.

[0818] The precipitated fluorine-containing elastomer is washed with water to remove a small amount of impurities such as buffer solution and salt in the fluorine-containing elastomer, and then dried.

[0819] The drying is preferably performed at 40°C to 200°C, more preferably at 60°C to 180°C, and even more preferably at 80°C to 150°C.

[0820] The fluorinated elastomer obtained by the production method of the present invention can be made into a fluorinated elastomer composition by adding a crosslinking agent, a filler, etc. The type and amount of the crosslinking agent and the filler are not particularly limited and can be used within a known range.

[0821] The method for obtaining the fluorinated elastomer composition is not particularly limited as long as a method is used that can uniformly mix the fluorinated elastomer with the crosslinking agent, filler, etc. For example, the following method can be mentioned: a powder obtained by precipitating the fluorinated elastomer alone and other additives and compounding agents as required are kneaded using a kneading machine such as an open mill.

[0822] When the fluorinated elastomer is an uncrosslinked elastomer, its crosslinking system may include, for example, a peroxide crosslinking system, a polyol crosslinking system, a polyamine crosslinking system, etc., preferably at least one selected from the group consisting of a peroxide crosslinking system and a polyol crosslinking system. From the aspect of chemical resistance, a peroxide crosslinking system is preferred, and from the aspect of heat resistance, a polyol crosslinking system is preferred.

[0823] Therefore, as the cross-linking agent, at least one cross-linking agent selected from the group consisting of a polyol cross-linking agent and a peroxide cross-linking agent is preferred, and a peroxide cross-linking agent is more preferred.

[0824] The amount of the crosslinking agent may be appropriately selected depending on the type of the crosslinking agent, etc., and is preferably 0.2 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass, based on 100 parts by mass of the fluorinated elastomer composition.

[0825] Peroxide crosslinking can be performed by using an uncrosslinked elastomer capable of peroxide crosslinking as the fluoroelastomer and an organic peroxide as the crosslinking agent.

[0826] The uncrosslinked elastomer capable of being crosslinked by peroxide is not particularly limited, as long as it is an uncrosslinked elastomer having a site capable of being crosslinked by peroxide. The site capable of being crosslinked by peroxide is not particularly limited, and examples thereof include a site having an iodine atom, a site having a bromine atom, and the like.

[0827] The organic peroxide may be any organic peroxide that can easily generate peroxide radicals in the presence of heat or a redox system, and examples thereof include 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α,α-bis(tert-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, tert-butylbenzene peroxide, tert-butyl maleate, tert-butyl peroxyisopropyl carbonate, and tert-butyl perbenzoate. Among these, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne are preferred.

[0828] The amount of the organic peroxide compounded is preferably from 0.1 to 15 parts by mass, more preferably from 0.3 to 5 parts by mass, based on 100 parts by mass of the fluorinated elastomer.

[0829] When the crosslinking agent is an organic peroxide, the fluorinated elastomer composition preferably further comprises a crosslinking aid. Examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate (TAIC), 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, N,N′-m-phenylene bismaleimide, diallyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl) -1,3,5-triazine-2,4,6-trione), tris(diallylamine)-s-triazine, N,N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N,N,N′,N′-tetraallylphthalamide, N,N,N′,N′-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tris(5-norbornene-2-methylene)cyanurate, triallylphosphite, etc. Among these, triallylisocyanurate (TAIC) is preferred from the viewpoint of excellent crosslinking properties, mechanical properties, and flexibility.

[0830] The amount of the crosslinking aid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7.0 parts by mass, and still more preferably 0.1 to 5.0 parts by mass relative to 100 parts by mass of the fluorinated elastomer. If the amount of the crosslinking aid is less than 0.01 parts by mass, the mechanical properties are reduced or the flexibility is reduced. If it exceeds 10 parts by mass, the heat resistance is poor and the durability of the molded product tends to be reduced.

[0831] Polyol crosslinking can be performed by using an uncrosslinked elastomer capable of polyol crosslinking as a fluorinated elastomer and a polyol as a crosslinking agent. The amount of the polyol compound in the polyol crosslinking system is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the uncrosslinked elastomer capable of polyol crosslinking. By making the amount of the polyol compound in this range, polyol crosslinking can be fully performed. More preferably, it is 0.02 to 8 parts by mass. More preferably, it is 0.03 to 4 parts by mass.

[0832] The above-mentioned uncrosslinked elastomer capable of being crosslinked by polyol is not particularly limited, as long as it is an uncrosslinked elastomer having a site capable of being crosslinked by polyol. The above-mentioned site capable of being crosslinked by polyol is not particularly limited, and examples thereof include a site having a vinylidene fluoride (VdF) unit. As a method for introducing the above-mentioned crosslinking site, a method of copolymerizing a monomer providing a crosslinking site during polymerization of the uncrosslinked elastomer can be mentioned.

[0833] As the polyhydroxy compound, a polyhydroxy aromatic compound is preferably used because of its excellent heat resistance.

[0834] The polyhydroxy aromatic compound is not particularly limited, and examples thereof include 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A), 2,2-bis(4-hydroxyphenyl)perfluoropropane (hereinafter referred to as bisphenol AF. Bisphenol AF can be obtained from, for example, Fujifilm-Wako Pure Chemical Industries, Ltd., Chuo Glass Co., Ltd., etc.), resorcinol, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxybis(4-hydroxyphenyl)propane, and the like. Benzene, stilbene-4,4'-diol, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis(4-hydroxyphenyl)butane (hereinafter referred to as bisphenol B), 4,4-bis(4-hydroxyphenyl)valeric acid, 2,2-bis(4-hydroxyphenyl)tetrafluorodichloropropane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ketone, tris(4-hydroxyphenyl)methane, 3,3',5,5'-tetrachlorobisphenol A, 3,3',5,5'-tetrabromobisphenol A, etc. These polyhydroxy aromatic compounds may be alkali metal salts, alkaline earth metal salts, etc. When the copolymer is precipitated using an acid, it is preferred not to use the above metal salts. The amount of the polyhydroxy aromatic compound blended is 0.1 to 15 parts by mass, preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the uncrosslinked elastomer.

[0835] When the crosslinking agent is a polyhydroxy compound, the fluorinated elastomer composition preferably further comprises a crosslinking accelerator. The crosslinking accelerator can accelerate the formation of intramolecular double bonds in the dehydrofluorination reaction of the polymer main chain and the addition of the polyhydroxy compound to the formed double bonds.

[0836] It should be noted that the cross-linking accelerator may be used in combination with an acid acceptor such as magnesium oxide or a cross-linking auxiliary agent.

[0837] As the crosslinking accelerator, an onium compound can be mentioned. Among the onium compounds, preferably at least one selected from the group consisting of ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines and monofunctional amine compounds is selected, and more preferably at least one selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts.

[0838] The quaternary ammonium salt is not particularly limited, and examples thereof include 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium iodide, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo[5 ,4,0]-7-undecenylium methyl sulfate, 8-ethyl-1,8-diazabicyclo[5,4,0]-7-undecenylium bromide, 8-propyl-1,8-diazabicyclo[5,4,0]-7-undecenylium bromide, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenylium chloride, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenylium Cyclo[5,4,0]-7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride (hereinafter referred to as DBU-B. DBU-B can be obtained, for example, from Fujifilm-Wako Pure Chemical Industries, Ltd., 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-(3-phenylpropyl)-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, etc. Among these, DBU-B is preferred from the aspects of crosslinking, mechanical properties and flexibility.

[0839] In addition, the quaternary phosphonium salt is not particularly limited, and examples thereof include tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, benzylphenyl(dimethylamino)phosphonium chloride, etc. Among these, benzyltriphenylphosphonium chloride (BTPPC) is preferred from the aspects of crosslinking, mechanical properties and flexibility.

[0840] As the crosslinking accelerator, a solid solution of a quaternary ammonium salt and bisphenol AF, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in Japanese Patent Application Laid-Open No. 11-147891 may be used.

[0841] The amount of the crosslinking accelerator is preferably 0.01 to 8.00 parts by mass, more preferably 0.02 to 5.00 parts by mass, relative to 100 parts by mass of the uncrosslinked elastomer. It is further preferably 0.03 to 3.00 parts by mass. If the crosslinking accelerator is less than 0.01 parts by mass, the crosslinking of the uncrosslinked elastomer is not fully carried out, and the heat resistance of the obtained molded product may be reduced. If it exceeds 8.00 parts by mass, there is a tendency that the molding processability of the above-mentioned fluorinated elastomer composition may be reduced, the elongation in the mechanical properties is reduced, and the flexibility is also reduced.

[0842] The acid acceptor is used to neutralize the acidic substances generated when the polyol is cross-linked. Specific examples thereof include magnesium oxide, calcium hydroxide (e.g., NICC5000 (manufactured by Inoue Lime Industry Co., Ltd.), CALDIC #2000, CALDIC #1000 (manufactured by Omi Chemical Industry Co., Ltd.)), calcium oxide, lead monoxide (lead oxide), zinc white, dibasic lead phosphite, hydrotalcite, etc., and preferably at least one selected from the group consisting of highly active magnesium oxide and low-active magnesium.

[0843] The polyamine crosslinking can be performed by using a polyamine-crosslinkable fluorine-containing elastomer as the fluorine-containing elastomer and a polyamine compound as the crosslinking agent.

[0844] The fluorinated elastomer capable of being crosslinked by polyamines is not particularly limited, as long as it is a fluorinated elastomer having a site capable of being crosslinked by polyamines. The site capable of being crosslinked by polyamines is not particularly limited, and examples thereof include sites having vinylidene fluoride (VdF) units. As a method for introducing the crosslinking site, a method of copolymerizing a monomer providing a crosslinking site during polymerization of the fluorinated elastomer can be cited.

[0845] Examples of the polyamine compound include hexamethylenediamine carbamate, N,N′-dicinnamyl-1,6-hexanediamine, and 4,4′-bis(aminocyclohexyl)methanecarbamate. Among these, N,N′-dicinnamyl-1,6-hexanediamine is preferred.

[0846] The fluorinated elastomer composition may contain at least one polyfunctional compound. A polyfunctional compound is a compound having two or more functional groups of the same or different structures in one molecule. As the functional group possessed by the polyfunctional compound, any functional group generally known to have reactivity, such as carbonyl, carboxyl, haloformyl, amide, olefin, amino, isocyanate, hydroxyl, epoxy, etc., may be used.

[0847] The above-mentioned fluorine-containing elastomer composition may be mixed with various additives commonly mixed with elastomers as needed, such as fillers, processing aids, plasticizers, colorants, stabilizers, adhesion promoters, mold release agents, conductivity-imparting agents, thermal conductivity-imparting agents, surface non-tackifiers, flexibility-imparting agents, heat resistance-improving agents, flame retardants, etc. These additives may be used in a range that does not impair the effects of the present invention.

[0848] Furthermore, a molded article can be obtained from the above-mentioned fluorinated elastomer composition.

[0849] The molded article can be obtained by molding and cross-linking the fluorinated elastomer composition. The fluorinated elastomer composition can be molded by a conventionally known method. The molding and cross-linking methods and conditions can be within the range of the methods and conditions known in the molding and cross-linking. The order of molding and cross-linking is not limited, and cross-linking can be performed after molding, molding can be performed after cross-linking, or molding and cross-linking can be performed simultaneously.

[0850] As molding methods, for example, compression molding using a mold, injection molding, etc. can be exemplified, but are not limited to these. As crosslinking methods, steam crosslinking, a common method of starting a crosslinking reaction by heating, radiation crosslinking, etc. can be used, among which a crosslinking reaction using heating is preferred. As specific crosslinking conditions that are not limited, they can be appropriately determined according to the type of crosslinking agent used, etc., usually within a temperature range of 140°C to 250°C and a crosslinking time of 1 minute to 24 hours.

[0851] The molded article of the present invention can be used as various parts in various fields such as the automobile industry, the aircraft industry, and the semiconductor industry.

[0852] Examples of the fields in which the invention is used include semiconductor-related fields, automobile fields, aircraft fields, aerospace and rocket fields, ship fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, printing fields such as printing machines, coating fields such as coating equipment, analytical instruments, meters and other analysis and physical and chemical machinery fields, food equipment fields including food factory equipment and household products, beverage and food manufacturing equipment fields, pharmaceutical manufacturing equipment fields, medical parts fields, chemical drug transmission equipment fields, nuclear power plant equipment fields, steel fields such as iron plate processing equipment, general industrial fields, electrical fields, fuel cell fields, electronic parts fields, optical equipment parts fields, space equipment parts fields, petrochemical factory equipment fields, equipment parts fields for energy exploration and production of oil, natural gas, etc., oil refining fields, oil transportation equipment parts fields, and the like.

[0853] Examples of the use form of the molded article of the present invention include various sealing materials or gaskets such as rings, gaskets, washers, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and end seals, gas transport plate seals, wafer support seals, barrel seals, etc. As a sealing material, it can be used for applications requiring excellent non-stickiness and low friction.

[0854] In addition, it can also be used as pipes, hoses, rollers, various rubber rollers, flexible joints, rubber sheets, coatings, belts, shock absorbers, valves, valve seats, valve bodies, chemical-resistant coating materials, laminating materials, lining materials, etc.

[0855] It should be noted that the cross-sectional shapes of the above-mentioned rings, gaskets and seals can be various shapes, specifically, they can be shapes such as quadrilateral, O-shape, ferrule, etc., or they can be special shapes such as D-shape, L-shape, T-shape, V-shape, X-shape, Y-shape, etc.

[0856] In the above-mentioned semiconductor-related fields, it can be used for, for example, semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma display panel manufacturing equipment, plasma addressed liquid crystal panel manufacturing equipment, organic EL panel manufacturing equipment, field emission display panel manufacturing equipment, solar cell substrate manufacturing equipment, semiconductor conveying equipment, etc. As such equipment, there can be cited, for example, CVD equipment, gas control equipment such as semiconductor gas control equipment, dry etching equipment, wet etching equipment, plasma etching equipment, reactive ion etching equipment, reactive ion beam etching equipment, sputtering etching equipment, ion beam etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, plasma ashing equipment, cleaning equipment, ion implantation equipment, plasma CVD equipment, exhaust equipment, exposure equipment, grinding equipment, film forming equipment, dry etching cleaning equipment, UV / O3 cleaning equipment, ion beam cleaning equipment, laser beam cleaning equipment, plasma cleaning equipment, gas etching cleaning equipment, extraction equipment, etc. Cleaning equipment, Soxhlet extraction cleaning equipment, high-temperature and high-pressure extraction cleaning equipment, microwave extraction cleaning equipment, supercritical extraction cleaning equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, etc., photolithography machine, coating and developing equipment, CMP equipment, excimer laser exposure machine, reagent piping, gas piping, equipment for plasma treatment such as NF3 plasma treatment, O2 plasma treatment, fluorine plasma treatment, etc., thermal treatment film forming equipment, wafer conveying equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD process, equipment used in lamp annealing process, equipment used in reflow process, etc.

[0857] As specific usage forms in semiconductor-related fields, there can be cited various sealing materials such as gate valves, quartz windows, chambers, chamber covers, gates, bell jars, connectors, and pump O-rings or gaskets; various sealing materials, hoses or tubes such as O-rings for resist developers or stripping solutions; linings or coatings for resist developer tanks, stripping tanks, wafer cleaning tanks, and wet etching tanks; diaphragms for pumps; rollers for wafer conveyance; hoses for wafer cleaning solutions; sealing materials for clean equipment such as sealants for clean rooms; sealing materials for storage warehouses for storing semiconductor manufacturing equipment or devices such as wafers; diaphragms for transporting reagents used in the process of manufacturing semiconductors, etc.

[0858] In the above-mentioned automotive field, it can be used in the engine body, main motion system, valve system, lubrication and cooling system, fuel system, intake and exhaust system, transmission system of the drive system, control system of the chassis, brake system, or basic electrical components, control system electrical components, equipment electrical components and other electrical components, etc. It should be noted that the above-mentioned automotive field also includes automatic two-wheeled vehicles.

[0859] In the above-mentioned engine body or its peripheral devices, the molded product of the present invention can be used in various sealing materials that require heat resistance, oil resistance, fuel oil resistance, resistance to antifreeze for engine cooling, and steam resistance. As such sealing materials, there can be cited seals such as gaskets, shaft sealing devices, valve stem seals, or self-tightening seals, piston rings, open ring seals, mechanical seals, oil seals and other non-contact or contact type seals, bellows, diaphragms, hoses, tubes, as well as wires, cushioning materials, shockproof parts, various sealing materials used in AT devices, etc.

[0860] As specific usage forms in the above-mentioned fuel system, there can be cited O-rings used in fuel injectors, cold start injectors, quick connectors for fuel lines, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, pipe bodies of fuel pipes, connectors of fuel pipes, injectors, etc.; seals used in exhalation system manifolds, fuel filters, pressure regulating valves, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sending units, fuel injection devices, fuel high-pressure pumps, fuel line connection systems, pump timing control valves, suction control valves, solenoid valve subassemblies, fuel shut-off valves, etc.; canister solenoid valve seals, vehicle-mounted refueling gas recovery system (ORVR) valve seals, oil seals for fuel pumps, fuel transfer seals, fuel tank rollover valve seals, packing seals, injector seals, fuel filler cap seals, fuel filler cap valve seals; fuel hoses, fuel supply hoses, fuel return hoses, vapor hoses, exhaust port (ventilation) hoses, refueling hoses, refueling hoses, hoses in fuel tanks (in-tank hoses), vaporization Hoses such as control hoses, fuel inlet hoses, and fuel vent hoses for fuel filters; gaskets used in fuel filters, fuel line connection systems, etc., or flange gaskets used in carburetors, etc.; pipe materials for vapor recovery lines, fuel raw material delivery pipes, oil and gas ORVR lines, etc.; gas canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetors, sensors, composite air control devices (CAC), pulsation dampers, gas canisters, diaphragms used in automatic valves, etc., or pressure regulator diaphragms for fuel injection devices; fuel pumps Valves, carburetor needle valves, rollover check valves, check valves; exhaust ports (vents), pipes used in fuel tanks; tank gaskets for fuel tanks, etc., gaskets for the accelerator pump piston of the carburetor; fuel transmission shockproof components for fuel tanks; O-rings and diaphragms for controlling fuel pressure; accelerator pump leather cups; built-in fuel pump mounting brackets; injector gaskets for fuel injection devices; injector seals; needle valve core valves for carburetors; accelerator pump pistons for carburetors; valve seats for compound air control devices (CAC); fuel tank bodies; sealing components for solenoid valves, etc.

[0861] As specific usage forms in the above-mentioned brake system, there can be cited diaphragms used in vacuum boosters, hydraulic brake hoses, air brake devices, brake device chambers of air brake devices, etc.; hoses used in brake device hoses, brake oil hoses, vacuum brake device hoses, etc.; various sealing materials such as oil seals, O-rings, gaskets, brake device piston seals, etc.; atmospheric valves or vacuum valves for vacuum boosters, check valves for brake device valves; piston cups (rubber sealing cups) for master cylinders, and brake device sealing cups; protective covers for master cylinders or vacuum boosters of hydraulic brake devices, wheel cylinders of hydraulic brake devices, O-rings or grommets for anti-lock braking systems (ABS), etc.

[0862] Specific usage forms of the basic electrical components include insulators or sheaths of electric wires (wiring), pipes of wiring harness exterior components, grommets for connectors, and the like.

[0863] Specific usage forms of the material in control system electrical components include covering materials for various sensor lines.

[0864] Specific use forms in the above-mentioned equipment electrical components include O-rings, gaskets, cooler hoses, high-pressure air conditioning hoses, air conditioning hoses, gaskets for electronic throttle valve units, direct ignition plug protection covers, distributor diaphragms, etc. of automobile air conditioners. In addition, it can also be used in the bonding of electrical components.

[0865] As specific usage forms in the above-mentioned intake and exhaust systems, there can be cited gaskets used in intake manifolds, exhaust manifolds, etc., throttle body gaskets of throttle valves; diaphragms used in EGR (exhaust gas recirculation), squeeze control (BPT), exhaust valves, turbine exhaust valves, actuators, turbine actuators of variable geometry turbines (VTG), exhaust purification valves, etc.; EGR (exhaust gas recirculation) control hoses, emission control hoses, turbine oil hoses (supply) for turbochargers, turbine oil hoses (return), turbine air hoses, intercooler hoses, turbocharger hoses, hoses connecting turbine engines with intercoolers and compressors, exhaust gas hoses, intake hoses, turbine hoses, DPF (diesel particulate filter) sensor hoses and other hoses; air ducts or turbine air ducts; intake manifold gaskets; EGR sealing materials, AB valve anti-afterburning valve seats, (turbocharger, etc.) turbine shaft sealing devices, rocker covers used in automobile engines or sealing components used in groove components such as air intake manifolds, etc.

[0866] In addition, in exhaust gas control components, it can be used as a seal used in vapor recovery tanks, catalytic converters, exhaust gas sensors, oxygen sensors, etc., or a seal for the solenoid valve armature of vapor recovery and vapor tanks; intake system manifold gaskets, etc.

[0867] In addition, in diesel engine-related parts, it can be used as O-ring seals for direct injection injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, and diaphragms for boost compensators. It can also be used as O-rings, sealing materials, hoses, pipes, diaphragms used in urea SCR systems, or urea tank bodies and sealing materials for urea tanks in urea SCR systems.

[0868] Specific use forms in the transmission system include bearing seals, oil seals, O-rings, gaskets, torque converter hoses, and the like related to the transmission.

[0869] Other examples include transmission oil seals, transmission oil hoses for AT, ATF hoses, O-rings, gaskets, and the like.

[0870] It should be noted that the transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), and the like.

[0871] In addition, oil seals, gaskets, O-rings, and seals for manual or automatic transmissions, or oil seals, gaskets, O-rings, and seals for continuously variable transmissions (belt type or ring type), as well as seals for ATF linear solenoid valves, oil hoses for manual transmissions, ATF hoses for automatic transmissions, CVTF hoses for continuously variable transmissions (belt type or ring type), etc. can also be mentioned.

[0872] Specific usage forms in the steering system include power steering oil hoses, high-pressure power steering hoses, and the like.

[0873] Examples of the gasket used in the engine body of an automobile engine include cylinder head gaskets, cylinder head cover gaskets, oil pan gaskets, general gaskets and other gaskets, O-rings, gaskets, timing belt cover gaskets and other seals, control hoses and other hoses, vibration-proof rubbers for engine mounts, control valve diaphragms, camshaft oil seals and the like.

[0874] In the main motion system of automobile engines, it can be used for crankshaft seals, camshaft oil seals and other shaft sealing devices.

[0875] In the valve actuation system of automobile engines, it can be used for the valve stem oil seal device of the engine valve, the valve seat of the butterfly valve, etc.

[0876] In the lubrication and cooling system of automobile engines, it can be used for oil cooler hoses, oil return hoses, sealing washers of oil coolers, water hoses around radiators, radiator seals, radiator washers, radiator O-rings, vacuum pump oil hoses of vacuum pumps, etc., as well as radiator hoses, radiator water tanks, oil pressure diaphragms, fan connection seals, etc.

[0877] Thus, as a specific example of use in the automotive field, there can be cited engine base gaskets, oil pan gaskets, manifold gaskets, seals for oxygen sensors, oxygen sensor bushings, seals for nitrogen oxide (NOx) sensors, nitrogen oxide (NOx) sensor bushings, seals for sulfur oxide sensors, seals for temperature sensors, temperature sensor bushings, seals for diesel particulate filter sensors, diesel particulate filter sensor bushings, injector O-rings, injector gaskets, O-rings or diaphragms for fuel pumps, gear box seals, power piston gaskets, cylinder liner seals, valve stem seals, static valve stem seals, dynamic valve stem seals, front pump seals for automatic transmissions, rear axle pinion seals, gaskets for universal joints, pinion seals for speedometers, piston cups for foot brakes, O-rings for torque transmission devices. ring or oil seal device, seal or bearing seal of exhaust gas reburning device, hose for reburning device, diaphragm for carburetor sensor, anti-vibration rubber (engine bracket, exhaust part, muffler hanging rubber, suspension bushing, center bearing, support rubber bumper, etc.), anti-vibration rubber for suspension (support rod assembly, bushing, etc.), anti-vibration rubber for drive system (damper, etc.), fuel hose, EGR pipe or hose, double-chamber parallel-acting carburetor pipe, core valve of carburetor needle valve, flange gasket of carburetor, oil hose, oil cooler hose, ATF hose, cylinder head gasket, water pump seal, gear box seal, needle valve plate, reed of motorcycle reed valve, oil seal device for automobile engine, seal of gasoline hose gun, seal for automobile air conditioner, rubber hose for engine internal cooler, fuel delivery path connector device (fuel line connector systems), CAC valves, needle plates, wires around engines, refueling hoses, car air conditioner O-rings, intake gaskets, fuel tank materials, diaphragms for distributors, hoses, clutch hoses, PS hoses, AT hoses, vacuum booster hoses, heater hoses, air conditioning hoses, ventilation hoses, fuel filler caps, PS rack seals, rack and pinion boots, CVJ boots, ball joint dust covers, pillar dust covers, weather strips, glass runners, center unit gaskets, body side seals, bumper rubber, door locks, instrument panel insulators, high-tension wires, flat belts, multi-V belts, synchronous toothed belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms or plungers for LPG car regulators, diaphragms or valves for CNG car regulators, DME-compatible rubber parts, automatic tensioning diaphragms or boots, diaphragms or valves for idle speed control, actuators for automatic speed control, diaphragms for negative pressure pumps, check valves or plungers, OPSDiaphragms or O-rings, gasoline pressure relief valves, O-rings or gaskets for engine cylinder liners, O-rings or gaskets for wet cylinder liners, seals or gaskets for differential gears (seals or gaskets for gear oil), seals or gaskets for power steering devices (seals or gaskets for PSF), seals or gaskets for shock absorbers (seals or gaskets for SAF), seals or gaskets for constant velocity joints, seals or gaskets for wheel bearings, coating agents for metal washers, caliper seals, protective covers, wheel bearing seals, bladders used in vulcanization molding of tires, etc.

[0878] In the above-mentioned aircraft field, aerospace and rocket field, and ship field, it can be used particularly in fuel systems and lubricating oil systems.

[0879] In the above-mentioned aircraft field, it can be used as, for example, various sealing parts for aircraft, various parts for aircraft for aircraft oil purposes, jet engine valve stem seals, gaskets or O-rings, rotating shaft seals, gaskets for hydraulic equipment, firewall seals, fuel supply hoses, gaskets or O-rings, aircraft cables, oil seals or shaft seals, etc.

[0880] In the above-mentioned aerospace and rocket fields, it can be used as, for example, lip seals, diaphragms, O-rings, or O-rings resistant to gas turbine engine oil, anti-vibration pads for missile ground control, etc. for spacecraft, jet engines, missiles, etc.

[0881] In addition, in the field of ships, it can be used as, for example, a stern seal for a propeller drive shaft, a valve stem seal for intake and exhaust of a diesel engine, a valve seal for a butterfly valve, a valve seat and a shaft seal for a butterfly valve, a shaft seal for a butterfly valve, a stern pipe seal, a fuel hose, a gasket, an O-ring for an engine, a ship cable, a ship oil seal device, a ship shaft seal device, etc.

[0882] In the chemical field such as chemical plants and the pharmaceutical field such as pharmaceuticals, the present invention can be used in processes requiring high chemical resistance, for example, in the production process of pharmaceuticals, agricultural chemicals, coatings, resins and other chemical products.

[0883] As specific forms of use in the above-mentioned chemical and pharmaceutical fields, there can be cited chemical devices, pumps or flow meters for chemicals, piping for chemicals, heat exchangers, pesticide sprayers, pesticide delivery pumps, gas piping, fuel cells, analytical instruments or physical and chemical instruments (for example, columns and accessories of analytical instruments and meters), shrink joints of flue gas desulfurization devices, seals used in nitric acid plants, turbines of power plants, etc., seals used in medical sterilization processes, seals for electroplating solutions, seals for pulleys for papermaking, joint seals for wind tunnels; O-rings used in chemical devices such as reactors and mixers, analytical instruments or meters, chemical pumps, pump housings, valves, rotary meters, etc., O-rings for mechanical seals, O-rings for compressor seals; gaskets used in high-temperature vacuum dryers, gas chromatographs or pH meter pipe joints, etc., sulfuric acid manufacturing Glass cooler seals for devices; diaphragms used in diaphragm pumps, analytical instruments or physical and chemical instruments; gaskets used in analytical instruments and meters; bushings (metal hoops) used in analytical instruments or meters; valve seats; U-shaped sealing leather cups; linings used in chemical devices, gasoline tanks, wind tunnels, etc., and corrosion-resistant linings of acid-resistant aluminum processing tanks; coatings of masking fixtures for plating; valve parts of analytical instruments or physical and chemical instruments; expansion joints in flue gas desulfurization plants; acid-resistant hoses for concentrated sulfuric acid, chlorine gas delivery hoses, oil-resistant hoses, rainwater drainage hoses for benzene or toluene storage tanks; chemical-resistant tubes or medical tubes used in analytical instruments or physical and chemical instruments; trichloroethylene-resistant rollers or dyeing rollers for fiber dyeing; suppositories for pharmaceuticals; rubber plugs for medical use; reagent bottles, reagent cans, bags, and pharmaceutical containers; protective gear such as gloves or boots that are resistant to strong acids and solvents, etc.

[0884] In the above-mentioned photographic fields such as developing machines, printing fields such as printing machinery, and coating fields such as coating equipment, the present invention can be used as rollers, belts, seals, valve components, etc. of dry copying machines.

[0885] As specific usage forms in the above-mentioned photographic field, printing field and coating field, there can be mentioned the surface layer of the transfer roller of a copier, the cleaning scraper of a copier, and the belt of a copier; rollers (such as fixing rollers, crimping rollers, pressure rollers, etc.) and belts used for OA equipment such as copiers, printers, fax machines, etc.; rollers, roller scrapers, and belts of PPC copiers; rollers of film developers and X-ray film developers; printing rollers, scrapers, tubes, valve parts, and belts of printing machinery; ink tubes, rollers, and belts of printers; coating rollers, scrapers, tubes, and valve parts of coating and coating equipment; developing rollers, gravure rollers, guide rollers, and guide rollers of a magnetic tape manufacturing coating production line, and gravure rollers and coating rollers of a magnetic tape manufacturing coating production line.

[0886] In the field of food equipment including food factory equipment and household products, the invention can be used in food manufacturing process, food conveyor or food storage.

[0887] Specific use forms in the above-mentioned food equipment field include seals for plate heat exchangers, solenoid valve seals for vending machines, gaskets for pots and jars, gaskets for sewage pipes, gaskets for pressure cookers, seals for water heaters, gaskets for heat exchangers, diaphragms or gaskets for food processing equipment, rubber materials for food processing equipment (e.g., various seals such as heat exchanger gaskets, diaphragms, O-rings, piping, hoses, sanitary gaskets, valve gaskets, and filling gaskets used as joints between the mouth of a bottle and a filler during filling), etc. In addition, gaskets, gaskets, pipes, diaphragms, hoses, joint sleeves, etc. used in products such as alcoholic beverages and cold drinking water, filling devices, food sterilization devices, brewing devices, water heaters, various automatic food vending machines, etc. can also be cited.

[0888] In the field of nuclear power plant equipment, it can be used for check valves and pressure reducing valves around nuclear reactors, seals for uranium hexafluoride enrichment devices, and the like.

[0889] Specific usage forms in the above-mentioned general industrial field include sealing materials for hydraulic equipment such as working machinery, construction machinery, and hydraulic machinery; seals or bearing seals for hydraulic and lubricating machinery; sealing materials used in spindles, etc.; seals used in windows of dry cleaning equipment, etc.; seals or (vacuum) valve seals for particle cyclotron accelerators, seals for proton accelerators, seals for automatic packaging machines, diaphragms for pumps used in sulfur dioxide or chlorine analyzers in the air (pollution testers), linings for snake pumps, rollers or belts for printing presses, belts (conveyor belts) for conveyors, squeeze rollers for pickling of iron plates, etc., cables for robots, solvent squeeze rollers for aluminum rolling pipelines, O-rings for couplers, acid-resistant buffer materials, dust seals or lip rubbers for sliding parts of cutting machines, gaskets for water-containing waste incinerators, friction materials, and metal or rubber covering materials. In addition, it can also be used as gaskets or sealing materials for equipment used in papermaking processes, sealants for filter units for clean rooms, sealants for buildings, fuel containers for small generators and lawn mowers, etc., and pre-coated metals obtained by applying a primer to metal plates.

[0890] As a specific application form in the above-mentioned steel field, iron plate processing rolls of iron plate processing equipment and the like can be cited.

[0891] As specific forms of use in the above-mentioned electrical field, there can be cited insulating oil caps for Shinkansen, ventilation seals for liquid-sealed transformers, seals for transformers, jackets for oil well cables, seals for ovens such as electric furnaces, window frame seals for microwave ovens, sealing materials used when bonding wedges and grooves of CRTs, sealing materials for halogen lamps, fixing agents for electrical components, sealing materials for terminal treatment of sheath heaters, and sealing materials used for insulation and moisture-proof treatment of lead terminals of electrical equipment. In addition, it can also be used for covering materials such as oil-resistant and heat-resistant wires, high heat-resistant wires, chemical-resistant wires, high-insulation wires, high-voltage transmission lines, cables, wires used in geothermal power generation devices, and wires used around automobile engines. It can also be used for oil seals or shaft seals for vehicle cables. Furthermore, it can also be used for electrical insulating materials (such as insulating spacers for various electrical equipment, insulating tapes used in joints or terminal parts of cables, materials used in heat-shrinkable tubes, etc.), and electrical and electronic equipment materials used in high-temperature atmospheres (such as lead wire materials for motors, wire materials around high-temperature furnaces).

[0892] In the above-mentioned fuel cell field, it can be used as a sealing material between electrodes and between electrodes and separators in solid polymer fuel cells, phosphate fuel cells, etc., a seal or gasket for piping of hydrogen, oxygen, generated water, etc., a separator, etc.

[0893] In the above-mentioned electronic component field, it can be used as a raw material for heat dissipation materials, a raw material for electromagnetic wave shielding materials, a gasket for a computer hard disk drive (magnetic recording device), etc. In addition, it can also be used as a buffer rubber (collision brake) for a hard disk drive, a sealant, a coating material for quartz of an optical fiber, a film or sheet such as an optical fiber coating material, an anti-scattering material for electronic components, light bulbs, etc., a gasket for a computer, a cooling hose for a large computer, a gasket or an O-ring for a secondary battery, especially a lithium secondary battery, a connector, a damper, etc.

[0894] In the field of chemical transport equipment, the present invention can be used for safety valves or shipping valves of trucks, trailers, tank trucks, ships, and the like.

[0895] In the field of oil, natural gas and other energy exploration and mining equipment components, it is used as various sealing materials used in the mining of oil, natural gas, etc., protective covers for electrical connectors used in oil wells, etc.

[0896] As specific usage forms in the field of the above-mentioned energy detection and mining equipment components, there can be cited drill bit seals, pressure regulating diaphragms, seals for horizontal excavation motors (stators), stator bearing (shaft) seals, sealing materials used in blowout preventers (BOPs), sealing materials used in rotary blowout preventers (drill pipe scrapers), sealing materials or gas-liquid connectors used in MWD (real-time mining information detection system), logging tool seals (such as O-rings, seals, gaskets, gas-liquid connectors, protective covers, etc.) used in logging devices (logging equipment), expansion packers or completion packers and the packer seals used therein, seals or gaskets used in cement grouting devices, Seals used in perforators (perforating devices), seals used in mud pumps, gaskets or motor liners, underground audio detector covers, U-shaped sealing cups, composite mounted sealing cups, rotary seals, laminated elastic bearings, flow control seals, sand volume control seals, safety valve seals, hydraulic fracturing equipment (fracturing equipment), linear packers or linear hanger seals or gaskets, wellhead seals or gaskets, chokes or valve seals or gaskets, LWD (logging while drilling) sealing materials, diaphragms used in oil exploration / oil drilling applications (such as diaphragms for lubricating oil supply to oil drilling fluid pools, etc.), gate valves, electronic protective covers, perforating gun sealing elements, etc.

[0897] In addition, it can also be used as seam sealants in kitchens, bathrooms, toilets, etc.; adhesive tapes for outdoor tents; seals for stamp materials; rubber hoses and Freon-resistant rubber hoses for gas heat pumps; films, liners, and weather-resistant covers for agriculture; and cans such as laminated steel sheets used in the construction or home appliance fields.

[0898] In addition, it can also be used as an article bonded to a metal such as aluminum. Such a use form includes, for example, door seals, gate valves, swing valves, solenoid valve tips, and metal-bonded piston seals or diaphragms, metal gaskets, and other metal-bonded rubber parts.

[0899] In addition, it can also be used for rubber parts, brake pads, brake blocks, etc. in bicycles.

[0900] In addition, as one form of the molded article of the present invention, a belt can be mentioned. Such a belt is also one of the present invention.

[0901] As the above-mentioned belts, the following belts can be exemplified. As power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.), conveyor belts (conveyor belts), there can be cited: flat belts used in various high-temperature locations such as around engines of agricultural machinery, working machinery, industrial machinery, etc.; conveyor belts used to convey loose or granular materials such as coal, gravel, sand, ore, wood chips, etc. in a high-temperature environment; conveyor belts used in steel mills such as blast furnaces; conveyor belts used in applications exposed to high-temperature environments such as precision equipment assembly factories and food factories; V-belts or V-ribbed belts for agricultural machinery, general equipment (such as OA equipment, printing machinery, business dryers, etc.), automobiles, etc.; transmission belts for conveying robots; toothed belts such as transmission belts for food machinery and working machinery; toothed belts used in automobiles, OA equipment, medical use, printing machinery, etc.

[0902] In particular, as a toothed belt for automobiles, a synchronous toothed belt is a representative example.

[0903] The above-mentioned belt may be a single-layer structure or a multi-layer structure.

[0904] In the case of a multi-layer structure, the tape may be composed of a layer formed of the molded article and a layer formed of another material.

[0905] In the multi-layered belt, as the layer formed of other materials, there can be mentioned a layer formed of other rubbers, a layer formed of thermoplastic resins, various fiber-reinforced layers, canvas, metal foil layers, and the like.

[0906] The molded article of the present invention can also be used for industrial anti-vibration pads, anti-vibration pads, railway slab mats, pads, automotive anti-vibration rubbers, etc. Examples of automotive anti-vibration rubbers include anti-vibration rubbers for engine mounts, motor assembly, component assembly, support rod assembly, bushings, dampers, silencer suspension rubbers, center bearings, and the like.

[0907] In addition, other usage forms include flexible joints, connection parts such as expansion joints, protective covers, grommets, etc. In the field of ships, for example, marine pumps, etc. can be mentioned.

[0908] Connecting parts refer to joints used in piping and piping equipment, which can be used for the following purposes: preventing vibration and noise generated by the piping system; absorbing expansion or displacement caused by temperature changes and pressure changes; absorbing dimensional changes; alleviating and preventing the impact caused by earthquakes and foundation subsidence; etc.

[0909] Flexible joints and expansion joints can be preferably used as complex-shaped molded products such as for shipbuilding piping, mechanical piping for pumps and compressors, piping for chemical equipment, electrical piping, civil engineering / water pipe piping, and automobiles.

[0910] The protective cover can be preferably used as complex-shaped molded bodies such as constant velocity joint protective covers, dust covers, rack and pinion control protective covers, bolt protective covers, piston protective covers, and other automotive protective covers, agricultural machinery protective covers, industrial vehicle protective covers, construction machinery protective covers, hydraulic machinery protective covers, air compressor machinery protective covers, centralized lubrication machine protective covers, liquid transportation protective covers, fire protection covers, various liquefied gas transportation protective covers, and other various industrial protective covers.

[0911] The molded article of the present invention can also be used as diaphragms for filter presses, diaphragms for blowers, diaphragms for water supply, diaphragms for liquid storage tanks, diaphragms for pressure switches, diaphragms for accumulators, diaphragms for air springs such as hangers, and the like.

[0912] The molded article of the present invention can also be used as a cushioning material for hot press molding when producing decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc. using melamine resins, phenol resins, epoxy resins, etc.

[0913] The molded article of the present invention can also contribute to the waterproofing of various supporting bodies such as gaskets associated with weapons and protective clothing for protecting against contact with aggressive chemical agents.

[0914] In addition, the present invention can be used for various sealing materials such as O (square) rings, V-rings, X-rings, gaskets, washers, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and end seals, gas transfer plate seals, wafer support seals, and roller seals used for sealing and encapsulating lubricating oils (engine oils, transmission oils, gear oils, etc.), fuel oils, and greases (especially urea greases) containing amine additives (especially amine additives used as antioxidants and detergent dispersants) used in transportation equipment such as automobiles and ships, etc., and can also be used as pipes, hoses, various rubber rollers, coatings, belts, valve bodies of valves, etc. In addition, it can be used as a laminating material and a lining material.

[0915] It can also be used as a covering material for heat-resistant and oil-resistant electric wires used in lead wires of sensors that come into contact with transmission oil and / or engine oil of internal combustion engines of automobiles and the like to detect the oil temperature and / or oil pressure thereof, and in high-temperature oil atmospheres such as in the oil pan of an automatic transmission or engine.

[0916] In addition, the molded article of the present invention may be used after forming a vulcanized coating on it. Specifically, the molded article may be used in non-adhesive oil-resistant rollers for copiers, weather strips for weatherproofing and anti-icing, rubber stoppers for infusions, rubber stoppers for vials, anti-adhesive agents, non-adhesive light conveyor belts, anti-adhesive coatings for flat washers of automobile engine mounts, coating of synthetic fibers, bolt parts or joints with a thin gasket coating layer, and the like.

[0917] It should be noted that the use of the molded article of the present invention as a component of an automobile also includes use as a component of a motorcycle having the same structure.

[0918] Examples of the fuel in the automobile-related applications include light oil, gasoline, and diesel engine fuel (including biodiesel fuel).

[0919] Among them, the molded article of the present invention is particularly suitable as a sealing material, a sliding part or a non-adhesive part.

[0920] The production method of the present invention can also obtain a composition comprising a fluorinated elastomer and a hydrocarbon-based surfactant (B), wherein the fluorinated elastomer comprises a structural unit derived from a fluorinated compound (A) containing a functional group capable of reacting in free radical polymerization and a hydrophilic group. In addition, the present invention also relates to a composition characterized in that it comprises a fluorinated elastomer and a hydrocarbon-based surfactant (B), wherein the fluorinated elastomer comprises a structural unit derived from a fluorinated compound (A) containing a functional group capable of reacting in free radical polymerization and a hydrophilic group.

[0921] The composition of the present invention preferably contains 1 ppm to 1000 ppm of a hydrocarbon surfactant (B) relative to the above-mentioned fluorinated elastomer. The content of the hydrocarbon surfactant is more preferably 900 ppm or less, further preferably 800 ppm or less, and particularly preferably 700 ppm or less relative to the fluorinated elastomer. In addition, it can be 5 ppm or more, or 10 ppm or more.

[0922] The content of the hydrocarbon-based surfactant (B) in the composition of the present invention can be measured by liquid chromatography.

[0923] The fluorinated elastomer is not particularly limited except that it contains the structural unit derived from the fluorinated compound (A), and examples thereof include copolymers of two or more fluorinated monomers, or copolymers of a fluorinated monomer and a non-fluorinated monomer, etc. The fluorinated compound (A), fluorinated monomer, and non-fluorinated monomer constituting the fluorinated elastomer are the same as those described in the manufacturing method of the present invention.

[0924] As the above-mentioned fluorinated elastomer, a fluorinated elastomer containing -CH2- in the main chain is preferred. As the fluorinated elastomer containing -CH2- in the main chain, the fluorinated elastomer described below can be cited. As the fluorinated elastomer containing -CH2- in the main chain, there is no particular limitation as long as it contains the chemical structure shown by -CH2-, and for example, elastomers containing structures such as -CH2-CF2-, -CH2-CH(CH3)-, and -CH2-CH2- can be cited, which can be introduced into the main chain of the fluorinated elastomer by, for example, polymerizing vinylidene fluoride, propylene, ethylene, etc.

[0925] The fluorinated elastomer may include, for example, vinylidene fluoride (VdF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, hexafluoroisobutylene, vinyl fluoride, iodine-containing fluorinated vinyl ether, formula (2)

[0926] CHX 1 =CX 2 Rf (2)

[0927] (Where X 1 and X 2 One of them is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) or other fluorine-containing monomer structural units such as fluorine-containing monomers (2).

[0928] The fluorine-containing elastomer is preferably selected from the group consisting of, for example, tetrafluoroethylene (TFE), vinylidene fluoride (VdF) and the formula (1):

[0929] CF2=CF-Rf a (1)

[0930] (Where Rf a -CF3 or -ORf b (Rf b It is a structural unit of at least one monomer selected from the group consisting of a perfluoroethylenically unsaturated compound represented by a perfluoroalkyl group having 1 to 5 carbon atoms (for example, hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), etc.).

[0931] More specifically, the fluorinated elastomers include VdF fluorinated elastomers, TFE / propylene (Pr) fluorinated elastomers, TFE / Pr / VdF fluorinated elastomers, ethylene (Et) / HFP fluorinated elastomers, Et / HFP / VdF fluorinated elastomers, Et / HFP / TFE fluorinated elastomers, Et / TFE / PAVE fluorinated elastomers, etc. Among these, VdF fluorinated elastomers, TFE / Pr fluorinated elastomers, TFE / Pr / VdF fluorinated elastomers, or Et / TFE / PAVE fluorinated elastomers are more preferred in terms of good heat aging resistance and oil resistance.

[0932] The VdF-based fluorinated elastomer is a fluorinated elastomer having VdF units. In the VdF-based fluorinated elastomer, the VdF units are preferably 20 mol% to 90 mol% of the total molar number of the VdF units and monomer units derived from other monomers, more preferably 40 mol% to 85 mol%, further preferably 45 mol% to 80 mol%, particularly preferably 50 mol% to 80 mol%.

[0933] Furthermore, other monomers in the VdF-based fluorinated elastomer are not particularly limited as long as they are copolymerizable with VdF, and for example, the above-mentioned fluorinated monomers can be used.

[0934] As the above-mentioned VdF-based fluorine-containing elastomer, it is preferred to have at least one copolymer selected from the group consisting of a VdF / HFP copolymer, a VdF / TFE / HFP copolymer, a VdF / CTFE copolymer, a VdF / CTFE / TFE copolymer, a VdF / PAVE copolymer, a VdF / TFE / PAVE copolymer, a VdF / HFP / PAVE copolymer, a VdF / HFP / TFE / PAVE copolymer, a VdF / TFE / Pr copolymer, a VdF / Et / HFP copolymer, and a VdF / copolymer of a fluorine-containing monomer represented by formula (2). In addition, as other monomers other than VdF, it is more preferred to have at least one monomer selected from the group consisting of TFE, HFP and PAVE.

[0935] Among them, at least one copolymer selected from the group consisting of VdF / HFP copolymers, VdF / TFE / HFP copolymers, VdF / copolymers of fluorinated monomers represented by formula (2), VdF / PAVE copolymers, VdF / TFE / PAVE copolymers, VdF / HFP / PAVE copolymers and VdF / HFP / TFE / PAVE copolymers is preferred, and at least one copolymer selected from the group consisting of VdF / HFP copolymers, VdF / HFP / TFE copolymers, VdF / copolymers of fluorinated monomers represented by formula (2) and VdF / PAVE copolymers is more preferred.

[0936] As the VdF / PAVE copolymer, a copolymer having a VdF / PAVE composition of (65 to 90) / (35 to 10) (mol %) is preferred.

[0937] In addition, it is also one of the preferred embodiments that the composition of VdF / PAVE is (50 to 78) / (50 to 22) (mol %).

[0938] As the VdF / TFE / PAVE copolymer, a copolymer having a composition of VdF / TFE / PAVE of (40 to 80) / (3 to 40) / (15 to 35) (mol %) is preferred.

[0939] As the VdF / HFP / PAVE copolymer, a copolymer having a composition of VdF / HFP / PAVE of (65 to 90) / (3 to 25) / (3 to 25) (mol %) is preferred.

[0940] The VdF / HFP / TFE / PAVE copolymer preferably has a composition of (40-90) / (0-25) / (0-40) / (3-35) (mol %) of VdF / HFP / TFE / PAVE, and more preferably has a composition of (40-80) / (3-25) / (3-40) / (3-25) (mol %).

[0941] As the VdF / fluorinated monomer (2) copolymer represented by formula (2), it is preferred that the VdF / fluorinated monomer (2) unit is (85-20) / (15-80) (mol%), and the monomer units other than VdF and the fluorinated monomer (2) are 0-50 mol% of the total monomer units. The mol% ratio of the VdF / fluorinated monomer (2) unit is more preferably (80-20) / (20-80). In addition, it is also preferred that the composition of the VdF / fluorinated monomer (2) unit is (78-50) / (22-50) (mol%).

[0942] It is also preferred that the ratio of VdF / fluorinated monomer (2) units is (85 to 50) / (15 to 50) (mol%), and that monomer units other than VdF and the fluorinated monomer (2) account for 1 to 50 mol% of the total monomer units. As monomers other than VdF and the fluorinated monomer (2), monomers exemplified as other monomers in the above-mentioned VdF-based fluorinated elastomers, such as TFE, HFP, PMVE, perfluoroethylvinyl ether (PEVE), PPVE, CTFE, trifluoroethylene, hexafluoroisobutylene, vinyl fluoride, Et, Pr, alkyl vinyl ether, and monomers providing crosslinking groups are preferred, and PMVE, CTFE, HFP, and TFE are more preferred.

[0943] The TFE / Pr-based fluorinated elastomer is a fluorinated copolymer composed of 45 mol% to 70 mol% of TFE and 55 mol% to 30 mol% of Pr. In addition to these two components, a specific third component may be contained.

[0944] As the specific third component, for example, fluorinated monomers such as fluorinated olefins other than TFE (for example, VdF, HFP, CTFE, perfluoro(butylethylene) etc.), fluorinated vinyl ethers (perfluoro(propyl vinyl ether), perfluoro(methyl vinyl ether) etc.), α-olefins (ethylene, 1-butene etc.), vinyl ethers (ethyl vinyl ether, butyl vinyl ether, hydroxybutyl vinyl ether etc.), vinyl esters (vinyl acetate, vinyl benzoate, vinyl crotonate, vinyl methacrylate etc.), hydrocarbon monomers, etc. may be included. The specific third component may be one kind or two or more kinds may be used in combination.

[0945] The TFE / Pr-based fluorinated elastomer preferably contains VdF. Among the TFE / Pr-based fluorinated elastomers, an elastomer composed of TFE, Pr and VdF is referred to as a TFE / Pr / VdF-based fluorinated elastomer.

[0946] The TFE / Pr / VdF-based fluorinated elastomer may further contain the above-mentioned specific third component in addition to VdF. The above-mentioned specific third component may be used alone or in combination of two or more.

[0947] The total content of the third component in the TFE / Pr-based fluorinated elastomer is preferably 35 mol % or less, more preferably 33 mol % or less, further preferably 31 mol % or less.

[0948] As the Et / HFP copolymer, the composition of Et / HFP is preferably (35 to 80) / (65 to 20) (mol %), and more preferably (40 to 75) / (60 to 25) (mol %).

[0949] In the Et / HFP / TFE copolymer, the composition of Et / HFP / TFE is preferably (35 to 75) / (25 to 50) / (0 to 15) (mol %), and more preferably (45 to 75) / (25 to 45) / (0 to 10) (mol %).

[0950] In the Et / TFE / PAVE copolymer, the composition of Et / TFE / PAVE is preferably (10-40) / (32-60) / (20-40) (mol %), and more preferably (20-40) / (40-50) / (20-30) (mol %). As PAVE, PMVE is preferred.

[0951] The fluorine-containing elastomer preferably contains a VdF unit, and a VdF / HFP copolymer or a VdF / HFP / TFE copolymer is particularly preferred. For example, a copolymer having a composition of (32 to 85) / (10 to 34) / (0 to 34) (mol %) of VdF / HFP / TFE is particularly preferred. The composition of VdF / HFP / TFE is more preferably (32 to 85) / (15 to 34) / (0 to 34) (mol %), and further preferably (47 to 81) / (17 to 29) / (0 to 26) (mol %).

[0952] For example, in the above-mentioned VdF / HFP copolymer, the composition of VdF / HFP is preferably (45-85) / (15-55) (mol %), more preferably (50-83) / (17-50) (mol %), further preferably (55-81) / (19-45) (mol %), and still more preferably (60-80) / (20-40) (mol %).

[0953] In the above-mentioned VdF / HFP / TFE copolymer, the composition of VdF / HFP / TFE is preferably (32 to 80) / (10 to 34) / (4 to 34) (mol %).

[0954] The fluorinated elastomer contains preferably 0.001 to 1.000 mol %, more preferably 0.001 to 0.700 mol %, further preferably 0.001 to 0.500 mol % of the structural units based on all monomer units.

[0955] The content of the structural unit derived from the fluorine-containing compound (A) can be measured by NMR, IR, elemental analysis or the like.

[0956] The fluorinated elastomers exemplified above are those composed mainly of monomers, and those obtained by copolymerizing a monomer providing a crosslinking group may be used. The monomer providing a crosslinking group is the same as that described in the production method of the present invention.

[0957] The above-mentioned fluorine-containing elastomer preferably contains a -CH2I structure. 1 H-NMR spectrum confirmed that it contained a -CH2I structure. The above-mentioned fluorine-containing elastomer containing a -CH2I structure can be obtained by iodine transfer polymerization.

[0958] The amount of the -CH2I structure in the fluorinated elastomer is preferably 0.05 mol% to 1.50 mol% relative to 100 mol% of the -CH2- structure. The amount of the -CH2I structure is more preferably 0.08 mol% or more, further preferably 0.12 mol% or more, more preferably 1.20 mol% or less, further preferably 1.00 mol% or less, and particularly preferably 0.80 mol% or less. The amount of the -CH2I structure can be 1 The H-NMR spectrum was obtained.

[0959] In addition, the above-mentioned fluorine-containing elastomer further preferably contains a -CF2CH2I structure. The above-mentioned fluorine-containing elastomer containing a -CF2CH2I structure can be obtained by producing a VdF-based fluorine-containing elastomer by iodine transfer polymerization.

[0960] The amount of the -CF2CH2I structure in the fluorine-containing elastomer is preferably 0.05 mol% to 1.50 mol% relative to 100 mol% of the -CH2- structure. The amount of the -CF2CH2I structure is more preferably 0.08 mol% or more, further preferably 0.12 mol% or more, more preferably 1.20 mol% or less, further preferably 1.00 mol% or less, and particularly preferably 0.80 mol% or less. The amount of the -CF2CH2I structure is calculated by A / B*100 from the integral value A of all peak intensities and the integral value B of all peak intensities, wherein the integral value A of all peak intensities is 1 The integrated value B of all peak intensities observed in the region of 3.75ppm to 4.05ppm of the chemical shift from -CH2I in the H-NMR spectrum is the integrated value of all peak intensities observed in the region of 2.3ppm to 2.7ppm and 2.9ppm to 3.75ppm of the chemical shift from -CH2-.

[0961] The composition of the present invention preferably contains substantially no fluorinated surfactant. In this specification, "substantially contains no fluorinated surfactant" means that the fluorinated surfactant is 10 ppm or less relative to the fluorinated elastomer. The content of the fluorinated surfactant is preferably 1 ppm or less, more preferably 100 ppb or less, further more preferably 10 ppb or less, further more preferably 1 ppb or less, and particularly preferably the fluorinated surfactant obtained by the measurement based on liquid chromatography-mass spectrometry (LC / MS / MS) is below the detection limit.

[0962] The amount of the fluorinated surfactant can be quantified by a known method. For example, it can be quantified by LC / MS / MS analysis. First, methanol is added to the composition, and the molecular weight information is selected from the LC / MS / MS spectrum of the resulting extract to confirm that it is consistent with the structural formula of the candidate surfactant.

[0963] Thereafter, aqueous solutions of five or more concentrations of the identified surfactant were prepared, and LC / MS / MS analysis was performed at each concentration to prepare a calibration curve with respect to the area.

[0964] The composition can be quantitatively measured by subjecting it to Soxhlet extraction with methanol and subjecting the extract to LC / MS / MS analysis.

[0965] That is, the content of fluorinated surfactant can be quantitatively determined by, for example, LC / MS / MS analysis. First, methanol is added to an aqueous dispersion, extracted, and the obtained extract is subjected to LC / MS / MS analysis. In order to further improve the extraction efficiency, Soxhlet extraction, ultrasonic treatment, etc. can be used for processing. The molecular weight information is selected from the obtained LC / MS / MS spectrum, and it is confirmed that it is consistent with the structural formula of the candidate fluorinated surfactant. Afterwards, an aqueous solution with a content of more than 5 levels of the confirmed fluorinated surfactant is prepared, and an LC / MS / MS analysis of the aqueous solution of each content is performed, and the relationship between the content and the area relative to the content is plotted to draw a calibration curve. In addition, using the calibration curve, the area area of ​​the LC / MS / MS chromatogram of the fluorinated surfactant in the extract can be converted into the content of the fluorinated surfactant.

[0966] Examples of the fluorinated surfactant include anionic fluorinated surfactants and the like.

[0967] The anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less in the portion excluding the anionic group.

[0968] The fluorine-containing surfactant may be a fluorine-containing surfactant having an anionic moiety with a molecular weight of 800 or less.

[0969] It should be noted that the above-mentioned "anionic part" refers to the part of the above-mentioned fluorinated surfactant other than the cation. For example, in the F(CF2) shown in the formula (I) described below n1 In the case of COOM, it is "F(CF2) n1 COO” part.

[0970] In addition, as the above-mentioned fluorinated surfactant, a fluorinated surfactant having a LogPOW of 3.5 or less can be cited. The above-mentioned LogPOW is the partition coefficient between 1-octanol and water, and is represented by LogP [wherein P represents the ratio of the fluorinated surfactant concentration in octanol to the fluorinated surfactant concentration in water when a fluorinated surfactant-containing octanol / water (1:1) mixed solution undergoes phase separation].

[0971] The above LogPOW is calculated as follows: On column: TOSOH ODS-120T column ( HPLC was performed on standard substances (heptanoic acid, octanoic acid, nonanoic acid and decanoic acid) with known octanol / water partition coefficients under the following conditions: (a) a column having a 100 μm column, a column having a 400 μm column, a column having a 200 μm column, a column having a 100 μm column, a column having a 2 ...

[0972] Specific examples of the fluorinated surfactant include U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 142541, U.S. Patent Application Publication No. 2008 / 0015319, and U.S. Patent No. 3250808. Fluorinated surfactants described in Japanese Unexamined Patent Application No. 3,271,341, Japanese Unexamined Patent Application No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, Japanese Unexamined Patent Application No. 2007-119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, and International Publication No. 2013 / 189826.

[0973] Examples of the anionic fluorinated surfactant include the following general formula (N 0 ):

[0974] X n0 -Rf n0 -Y 0 (N 0 )

[0975] (Where X n0 is H, Cl or and F. Rf n0 It is a chain, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H groups are replaced by F. The alkylene group may contain one or more ether bonds, and some of the H groups may be replaced by Cl. 0 is an anionic group).

[0976] Y 0 The anionic group may be -COOM, -SO2M or -SO3M, or may be -COOM or -SO3M.

[0977] M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group.

[0978] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li.

[0979] As R 7 , can be H or C 1-10 The organic group can also be H or C 1-4 The organic group can also be H or C 1-4 of alkyl.

[0980] M can be H, metal atom or NR 7 4, may also be H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4, and can also be H, Na, K, Li or NH4.

[0981] The above Rf n0 In the above formula (A), more than 50% of the H can be replaced by fluorine.

[0982] As the above general formula (N 0 ) can include:

[0983] The following general formula (N 1 ):

[0984] X n0 -(CF2) m1 -Y 0 (N 1 )

[0985] (Where X n0 is H, Cl and F, m1 is an integer from 3 to 15, Y 0 The compound represented by the following general formula (N 2 ):

[0986] R n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 )

[0987] (Where Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, and X n1 F or CF3, Y 0 The compound represented by the following general formula (N 3 ):

[0988] R n2 (CH2) m3 -(Rf n3 ) q -Y 0 (N 3 )

[0989] (Where Rf n2 is a partially or completely fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y 0 The compound represented by the following general formula (N 4 ):

[0990] R n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 )

[0991] (Where Rf n4 is a linear or branched partially or completely fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond, n1 and Y n2 The same or different, H or F, p is 0 or 1, Y 0 The compound represented by the above-defined substance); and the following general formula (N 5 ):

[0992] [Chemistry 20]

[0993]

[0994] (Where X n2 , X n3 and X n4 Rf may be the same or different and is H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond. n5 is a linear or branched partially or completely fluorinated alkylene group having 1 to 3 carbon atoms and may contain an ether bond, L is a connecting group, Y 0is the substance defined above. n2 , X n3 , X n4 and Rf n5 The total number of carbon atoms is 18 or less).

[0995] As the above general formula (N 0 ), more specifically, a perfluorocarboxylic acid (I) represented by the following general formula (I), an ω-H perfluorocarboxylic acid (II) represented by the following general formula (II), a perfluoropolyether carboxylic acid (III) represented by the following general formula (III), a perfluoroalkyl alkylene carboxylic acid (IV) represented by the following general formula (IV), a perfluoroalkoxy fluorocarboxylic acid (V) represented by the following general formula (V), a perfluoroalkyl sulfonic acid (VI) represented by the following general formula (VI), an ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), a perfluoroalkyl alkylene sulfonic acid (VIII) represented by the following general formula (VIII), an alkyl alkylene carboxylic acid (IX) represented by the following general formula (IX), a fluorocarboxylic acid (X) represented by the following general formula (X), an alkoxy fluorosulfonic acid (XI) represented by the following general formula (XI), a compound (XII) represented by the following general formula (XII), and a compound (XIII) represented by the following general formula (XIII).

[0996] The above perfluorocarboxylic acid (I) is represented by the following general formula (I):

[0997] F(CF2) n1 COOM(I)

[0998] (where n1 is an integer from 3 to 14, M is H, a metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is H or an organic group).

[0999] The above-mentioned ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II):

[1000] H(CF2) n2 COOM(II)

[1001] (wherein n2 is an integer of 4 to 15, and M is the substance defined above).

[1002] The above-mentioned perfluoropolyether carboxylic acid (III) is represented by the following general formula (III):

[1003] R 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM(III)

[1004] (Where Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is the substance defined above).

[1005] The above perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV):

[1006] R 2 (CH2) n4 R 3 COOM(IV)

[1007] (Where 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, n4 is an integer of 1 to 3, and M is the substance defined above).

[1008] The above alkoxy fluorocarboxylic acid (V) is represented by the following general formula (V):

[1009] R 4 -O-CY 1 Y 2 CF2-COOM(V)

[1010] (Where Rf 4 is a linear or branched partially or completely fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond, 1 and Y 2 are the same or different, are H or F, and M is the substance defined above).

[1011] The above perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI):

[1012] F(CF2) n5 SO3M(VI)

[1013] (wherein n5 is an integer of 3 to 14, and M is the substance defined above).

[1014] The above-mentioned ω-H perfluorosulfonic acid (VII) is represented by the following general formula (VII):

[1015] H(CF2) n6 SO3M(VII)

[1016] (wherein n6 is an integer of 4 to 14, and M is the substance defined above).

[1017] The above perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII):

[1018] R 5 (CH2)n7 SO3M(VIII)

[1019] (Where Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is the substance defined above).

[1020] The above alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX):

[1021] R 6 (CH2) n8 COOM(IX)

[1022] (Where Rf 6 It is a linear or branched partially or completely fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer of 1 to 3, and M is the substance defined above).

[1023] The above fluorocarboxylic acid (X) is represented by the following general formula (X):

[1024] R 7 -O-Rf 8 -O-CF2-COOM(X)

[1025] (Where Rf 7 is a linear or branched partially or completely fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond, Rf 8 is a linear or branched partially or completely fluorinated alkyl group having 1 to 6 carbon atoms, and M is the substance defined above).

[1026] The above alkoxy fluorosulfonic acid (XI) is represented by the following general formula (XI):

[1027] R 9 -O-CY 1 Y 2 CF2-SO3M(XI)

[1028] (Where Rf 9 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, which may be partially or completely fluorinated, 1 and Y 2 are the same or different, are H or F, and M is the substance defined above).

[1029] The above compound (XII) is represented by the following general formula (XII):

[1030] [Chemistry 21]

[1031]

[1032] Where, X1 , X 2 and X 3 Rf may be the same or different and is H, F and a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and may contain an ether bond. 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a connecting group, Y 0 is an anionic group).

[1033] Y 0 It can be -COOM, -SO2M or -SO3M, or -SO3M or COOM (wherein M is the substance defined above).

[1034] Examples of L include a single bond and a partially or completely fluorinated alkylene group having 1 to 10 carbon atoms which may include an ether bond.

[1035] The above compound (XIII) is represented by the following general formula (XIII):

[1036] R 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM(XIII)

[1037] (Where Rf 11 is a fluorinated alkyl group having 1 to 5 carbon atoms and containing chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is the substance defined above). Examples of compound (XIII) include CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10 CF2COONH4 (mixture with an average molecular weight of 750, wherein n9 and n10 are the numbers defined above).

[1038] The number average molecular weight Mn of the fluorinated elastomer is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 500,000, particularly preferably from 20,000 to 300,000.

[1039] The fluorine content of the fluorine-containing elastomer is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. The upper limit of the fluorine content is preferably 75% by mass or less, and more preferably 73% by mass or less.

[1040] The above fluorine content is based on 19 F-NMR, 1 The measured values ​​in H-NMR, elemental analysis, etc. were calculated.

[1041] The Mooney viscosity of the fluorine-containing elastomer at 100° C. is preferably 130 or less. The Mooney viscosity is more preferably 110 or less, and further preferably 90 or less. Furthermore, the Mooney viscosity is more preferably 10 or more, and further preferably 20 or more. Here, the Mooney viscosity is a value measured in accordance with JIS K 6300-1.2013.

[1042] The glass transition temperature of the fluorinated elastomer is preferably -50°C to 0°C. The glass transition temperature is more preferably -2°C or less, and further preferably -3°C or less. In addition, the glass transition temperature is more preferably -45°C or more, and further preferably -40°C or more. The glass transition temperature may be -10°C or more, or -9°C or more. Here, the glass transition temperature can be obtained as follows: using a differential scanning calorimeter (e.g., X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.), by heating 10 mg of a sample at 20°C / min to obtain a DSC curve, the glass transition temperature can be obtained from the DSC differential curve according to JIS K 6240:2011.

[1043] The iodine content of the fluorinated elastomer is preferably 0.05 to 1.0 mass %, more preferably 0.08 mass % or more, further preferably 0.10 mass % or more, and more preferably 0.8 mass % or less, further preferably 0.60 mass % or less.

[1044] The above iodine content can be obtained by elemental analysis.

[1045] Specifically, 5 mg of Na2SO3 was mixed with 12 mg of fluorine-containing elastomer, 30 mg of a substance obtained by mixing Na2CO3 and K2CO3 at a mass ratio of 1:1 was dissolved in 20 ml of pure water to obtain an absorption liquid, and the absorption liquid was burned in oxygen in a quartz flask, and after standing for 30 minutes, it can be measured using a Shimadzu 20A ion chromatograph. As a calibration curve, a KI standard solution, a solution containing 0.5 ppm of iodide ions, and a solution containing 1.0 ppm of iodide ions can be used.

[1046] The composition of the present invention may be mixed with a crosslinking agent, etc. In addition, the composition of the present invention may be mixed with various additives such as fillers, processing aids, plasticizers, colorants, stabilizers, adhesion aids, mold release agents, conductivity-imparting agents, thermal conductivity-imparting agents, surface non-sticking agents, flexibility-imparting agents, heat resistance-improving agents, flame retardants, etc., which are commonly added to elastomers as needed. These additives may be used as long as they do not impair the effects of the present invention.

[1047] Furthermore, a molded article can be obtained from the composition of the present invention.

[1048] The above-mentioned molded article can be obtained by molding the composition of the present invention and cross-linking. The above-mentioned composition can be molded by existing known methods. The methods and conditions for molding and cross-linking can be within the range of the methods and conditions known in the molding and cross-linking adopted. The order of molding and cross-linking is not limited, and cross-linking can be performed after molding, molding can be performed after cross-linking, or molding and cross-linking can be performed simultaneously.

[1049] As molding methods, for example, compression molding using a mold, injection molding, etc. can be exemplified, but are not limited to these. As crosslinking methods, steam crosslinking, a common method of starting a crosslinking reaction by heating, radiation crosslinking, etc. can be used, among which a crosslinking reaction using heating is preferred. As specific crosslinking conditions that are not limited, they can be appropriately determined according to the type of crosslinking agent used, etc., usually within a temperature range of 140°C to 250°C and a crosslinking time of 1 minute to 24 hours.

[1050] The above-mentioned molded article can be used for the same uses as those described for the molded article obtained from the above-mentioned fluorinated elastomer composition.

[1051] Example

[1052] Next, the present invention will be described with reference to Examples, but the present invention is not limited to the Examples.

[1053] Each numerical value in the examples was measured by the following method.

[1054] Mooney viscosity

[1055] The Mooney viscosity can be measured at 100° C. using a Mooney viscometer MV2000E manufactured by ALPHATECHNOLOGIES in accordance with JIS K 6300-1.2013.

[1056] Glass transition temperature

[1057] The glass transition temperature was determined from a DSC curve obtained by heating 10 mg of a sample at 20° C. / min using a differential scanning calorimeter (X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.) and from the DSC differential curve in accordance with JIS K6240:2011.

[1058] Copolymer composition

[1059] In the present specification, the content of each monomer constituting the fluorinated elastomer can be calculated by NMR, elemental analysis or the like.

[1060] Solid content concentration of aqueous dispersion

[1061] 1 g of the 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 expressed as a percentage.

[1062] Adhesion rate

[1063] The ratio of the mass of the polymer deposited on the polymerization tank after the completion of the polymerization to the total amount of the polymer (fluorinated elastomer) after the completion of the polymerization (the adhesion ratio on the polymerization tank) was determined by the following method.

[1064] The polymer deposits include: polymers that adhere to the inner wall of the polymerization tank or the stirring blades inside the polymerization tank after the aqueous dispersion is extracted from the polymerization tank after the polymerization is completed; and polymers that are freed from the aqueous dispersion by coagulation and float or precipitate. The mass of the polymer deposits is the mass after the water contained in the polymer deposits is dried and removed at 120°C.

[1065] Adhesion rate (mass %) = mass of polymer deposits / mass of obtained polymer (including deposits) × 100

[1066] The mass of the obtained polymer = the mass of the aqueous dispersion × the solid content concentration of the aqueous dispersion (mass %) / 100 + the mass of the attached matter

[1067] Average particle size

[1068] The average particle size of the fluorinated elastomer particles in the aqueous dispersion was measured by a dynamic light scattering method using ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.), and the average particle size (cumulative average particle size) was calculated by a cumulative method.

[1069] Particle count (number of fluoroelastomer particles in aqueous dispersion)

[1070] Calculate it by the following formula.

[1071] [Number 2]

[1072]

[1073] Here, the average particle size is the cumulative average particle size calculated by the above method, the number of polymer particles (the number of fluorine-containing elastomer particles) is the number per 1 cc of water, and the specific gravity is 1.8.

[1074] Iodine content

[1075] In this specification, the iodine content of the fluorine-containing elastomer is calculated by the following elemental analysis.

[1076] 5 mg of Na2SO3 was mixed with 12 mg of fluorine-containing elastomer, and 30 mg of a mixture of Na2CO3 and K2CO3 in a ratio of 1:1 (mass ratio) was dissolved in 20 ml of pure water to obtain an absorption solution. The absorption solution was burned in oxygen in a quartz flask, left for 30 minutes, and then measured using a Shimadzu 20A ion chromatograph. As a calibration curve, a KI standard solution, a solution containing 0.5 ppm of iodide ions, and a solution containing 1.0 ppm of iodide ions were used.

[1077] The amount of -CH2I structure relative to 100 mol% of -CH2- structure in the fluoroelastomer

[1078] Fluoroelastomer 1 The H-NMR spectrum was obtained.

[1079] Vulcanization conditions

[1080] The rubbery fluorinated copolymers (fluorinated elastomers) obtained in Examples 2 and 4 to 12 were kneaded in the proportions shown in Tables 4 and 7 to obtain fluorinated elastomer compositions. For the obtained fluorinated elastomer compositions, a vulcanization curve was obtained using a rubber vulcanization tester MDRH2030 (manufactured by M&K Co.) during primary press vulcanization to obtain the minimum viscosity (ML), maximum torque level (MH), induction time (T10) and positive vulcanization time (T90).

[1081] Mixing method: Roller mixing

[1082] Pressurized vulcanization: 160°C for 10 minutes

[1083] Oven curing: 4 hours at 180°C

[1084] It should be noted that the materials shown in Table 4 and Table 7 are as follows.

[1085] MT Carbon: Thermax N-990 made by Cancarb.Ltd.

[1086] TAIC: Triallyl isocyanurate, manufactured by TAIC Nippon Chemical Co., Ltd.

[1087] PERHEXA25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, manufactured by NOF Corporation

[1088] Normal physical properties

[1089] The 100% modulus (M100), tensile strength at break (TB), and elongation at break (EB) of a cross-linked molded product sheet (dumbbell No. 6 shaped test piece) produced in accordance with JIS K6251 were measured under normal conditions.

[1090] hardness

[1091] The hardness (Shore A) (peak value, 1 second, 3 seconds) of the cross-linked molded product (dumbbell No. 6 shaped test piece) was measured in accordance with JIS K6253.

[1092] Compression set

[1093] The compression set of the P-24 ring produced in accordance with JIS K6262 at 25% compression at 200° C. for 72 hours was measured.

[1094] The compound a used in the examples is a compound represented by the following formula.

[1095] CH2=CF-CF2OCF(CF3)CF2OCF(CF3)COONH4

[1096] In each example, a 50% by mass aqueous solution of compound a was used. The amount of compound a added described in each example is the amount of a 50% by mass aqueous solution of compound a.

[1097] The hydrocarbon-based surfactant b used in the examples is a compound represented by the following formula.

[1098] [Chemistry 22]

[1099]

[1100] Example 1

[1101] Into a SUS polymerization tank with an internal volume of 3 L, 1500 g of deionized water, 23.19 g of disodium hydrogen phosphate, 0.7 g of sodium hydroxide, 0.278 g of sodium lauryl sulfate, 0.077 g of compound a, and 0.4 g of disodium ethylenediaminetetraacetic acid dihydrate and 0.3 g of ferrous sulfate heptahydrate dissolved in 100 g of deionized water were added, the polymerization tank was sealed, and the system was replaced with nitrogen to remove oxygen. The polymerization tank was heated to 25° C., and monomers (initial monomers) were pressed into the mixture in the form of vinylidene fluoride [VDF] / tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] (=19 / 11 / 70 mol%) to 0.83 MPaG under stirring. Next, a polymerization initiator aqueous solution prepared by dissolving 6.000 g of ammonium persulfate (APS) in deionized water was pressed into the mixture with nitrogen. After that, a 2.5% by mass aqueous solution of sodium hydroxymethanesulfinate dihydrate (hereinafter referred to as Rongalite) was added to the polymerization tank to start the reaction. After that, a 2.5% by mass aqueous solution of Rongalite was continuously added to the polymerization tank using a plunger pump. When the internal pressure dropped to 0.80 MPaG as the polymerization progressed, a mixed monomer of VDF / TFE / HFP (=50 / 20 / 30 mol%) was added in such a way that the internal pressure was constant at 0.83 MPaG. When 12 g of the mixed monomer was added, 2.91 g of the diiodide compound I(CF2)4I was pressed into the polymerization tank with nitrogen. When 598 g of the mixed monomer was added, stirring was stopped and the pressure was released until the polymerization tank reached atmospheric pressure. The polymerization tank was cooled to obtain an aqueous dispersion having a solid content concentration of 24.3% by mass. The total amount of the Rongalite aqueous solution added was 73.0 g. The adhesion rate on the polymerization tank, the mass of the aqueous dispersion, the average particle size and the number of particles are shown in Table 1.

[1102] Aqueous aluminum sulfate solution was added to the aqueous dispersion to precipitate. The precipitate obtained was washed with water and dried to obtain a rubbery fluorinated copolymer. The Mooney viscosity of the rubbery fluorinated copolymer was ML1+10(100°C)=85.8 and the glass transition temperature was -5.4°C. The copolymer composition was investigated by NMR analysis, and as a result, VDF / TFE / HFP=53 / 21 / 26 (mol %). In addition, the iodine content of the fluorinated copolymer and the amount of -CH2I structure relative to 100 mol % of -CH2- structure are shown in Table 1.

[1103] Example 2

[1104] The experiment was carried out under the same conditions as in Example 1 except that the amount of the diiodide compound I(CF2)4I was changed to 3.20 g.

[1105] The polymerization tank was cooled to obtain an aqueous dispersion having a solid content concentration of 23.1% by mass. The total amount of the Rongalite aqueous solution added was 74.7 g. The adhesion rate on the polymerization tank, the mass of the aqueous dispersion, the average particle size and the number of particles are shown in Table 1.

[1106] Aqueous aluminum sulfate solution was added to the aqueous dispersion to precipitate. The precipitate obtained was washed with water and dried to obtain a rubbery fluorinated copolymer. The Mooney viscosity of the rubbery fluorinated copolymer was ML1+10(100°C)=50.2, and the glass transition temperature was -5.9°C. The copolymer composition was investigated by NMR analysis, and as a result, VDF / TFE / HFP=53 / 21 / 26 (mol %). In addition, the iodine content of the fluorinated copolymer and the amount of -CH2I structure relative to 100 mol % of -CH2- structure are shown in Table 1.

[1107] Example 3

[1108] Into a SUS polymerization tank with an internal volume of 3 L, 1500 g of deionized water, 23.19 g of disodium hydrogen phosphate, 0.7 g of sodium hydroxide, 0.278 g of hydrocarbon surfactant b, 0.077 g of compound a, and 0.4 g of disodium ethylenediaminetetraacetic acid dihydrate and 0.3 g of ferrous sulfate heptahydrate dissolved in 100 g of deionized water were added, the polymerization tank was sealed, and the system was replaced with nitrogen to remove oxygen. The polymerization tank was heated to 25° C., and monomers (initial monomers) were pressed into the mixture in the form of vinylidene fluoride [VDF] / tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] (=19 / 11 / 70 mol%) to 0.83 MPaG under stirring. Next, a polymerization initiator aqueous solution prepared by dissolving 6.000 g of ammonium persulfate (APS) in deionized water was pressed into the mixture with nitrogen. Afterwards, a 2.5% by mass aqueous solution of Rongalite was added to the polymerization tank to start the reaction. Afterwards, a 2.5% by mass aqueous solution of Rongalite was continuously added to the polymerization tank using a plunger pump. When the internal pressure dropped to 0.80 MPaG as the polymerization progressed, a mixed monomer of VDF / TFE / HFP (=50 / 20 / 30 mol%) was added in such a way that the internal pressure was constant at 0.83 MPaG. When 12 g of the mixed monomer was added, 2.91 g of the diiodide compound I(CF2)4I was pressed into the polymerization tank with nitrogen. When 594 g of the mixed monomer was added, stirring was stopped and the pressure was released until the polymerization tank reached atmospheric pressure. The polymerization tank was cooled to obtain an aqueous dispersion having a solid content concentration of 24.2% by mass. The total amount of the Rongalite aqueous solution added was 68.0 g. The adhesion rate on the polymerization tank, the mass of the aqueous dispersion, the average particle size and the number of particles are shown in Table 1.

[1109] Aqueous aluminum sulfate solution was added to the aqueous dispersion to precipitate. The precipitate obtained was washed with water and dried to obtain a rubbery fluorinated copolymer. The Mooney viscosity of the rubbery fluorinated copolymer was ML1...

Claims

1. A method for producing a fluorine-containing elastomer, characterized in that: The method comprises the following polymerization steps: in the presence of a fluorine-containing compound (A) having a functional group capable of reacting in free radical polymerization and a hydrophilic group and a hydrocarbon surfactant (B), emulsion polymerizing a fluorine-containing monomer in an aqueous medium to obtain a fluorine-containing elastomer; The amount of the hydrocarbon surfactant (B) is an amount corresponding to 3 ppm to 1000 ppm of the aqueous medium, and the emulsion polymerization is carried out in the presence of a redox initiator.

2. The manufacturing method according to claim 1, wherein: The fluorine-containing compound (A) is a compound having a radically polymerizable unsaturated bond-containing group as a functional group capable of reacting in radical polymerization.

3. The manufacturing method according to claim 1 or 2, wherein: The fluorine-containing compound (A) and the hydrocarbon-based surfactant (B) are compounds each containing an anionic and / or nonionic hydrophilic group.

4. The production method according to any one of claims 1 to 3, wherein The hydrophilic group of the fluorine-containing compound (A) is -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2, wherein M is H, a metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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.

5. The production method according to any one of claims 1 to 4, wherein The fluorine-containing compound (A) is a compound represented by the following formula (A): CX i X k =CX j R a -(CZ 1 Z 2 ) k -Y 3 (A) In the formula, X i , X j and X k Each independently represents F, Cl, H or CF3; Y 3 is a hydrophilic group; R a is a connecting group; Z 1 and Z 2 Each independently is H, F or CF3; k is 0 or 1; wherein X i , X k , X j , R a , Z 1 and Z 2 At least one of them contains a fluorine atom; wherein, when k is 0, R a A connecting group other than a single bond.

6. The production method according to any one of claims 1 to 5, wherein The fluorine-containing compound (A) is at least one selected from the group consisting of a monomer represented by the following general formula (5), a monomer represented by the following general formula (6), and a monomer represented by the following general formula (7). CX2=CY(-CZ2-O-Rf-Y 3 ) (5) In the formula, X is the same or different and is -H or -F, Y is -H, -F, alkyl or fluorinated alkyl, Z is the same or different and is -H, -F, alkyl or fluorinated alkyl; Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond; Y 3 is a hydrophilic group, CX2=CY(-O-Rf-Y 3 ) (6) In the formula, X is the same or different and is -H or -F, Y is -H, -F, alkyl or fluorinated alkyl, Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms; 3 Same as above, CX2=CY(-Rf-Y 3 ) (7) In the formula, X is the same or different and is -H or -F, Y is -H, -F, alkyl or fluorinated alkyl, Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond and having 2 to 100 carbon atoms; 3 Same as above.

7. The production method according to any one of claims 1 to 6, wherein The fluorine-containing compound (A) is at least one selected from the group consisting of a monomer represented by the following general formula (5b), a monomer represented by the following general formula (5c), and a monomer represented by the following general formula (5d). CH2=CF(-CF2-O-Rf-Y 3 )(5b) In the formula, Rf is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having 2 to 100 carbon atoms and having an ether bond; Y 3 is a hydrophilic group, CX 2 2=CFCF2-O-(CF(CF3)CF2O) n5 -CF(CF3)-Y 3 (5c) In the formula, each X 2 The same, represents F or H; n5 represents 0 or an integer from 1 to 10, Y 3 Same as above, CF2=CFCF2-O-Rf-Y 3 (5d) In the formula, Rf and Y 3 Same as above.

8. The production method according to any one of claims 1 to 7, wherein The hydrocarbon-based surfactant (B) is a surfactant represented by the following general formula (γ): R 14 -Y 3 (c) In the formula, R 14 represents an aliphatic hydrocarbon group which may or may not contain a carbonyl group; 3 It is a hydrophilic group.

9. The manufacturing method according to claim 8, wherein: Y of the general formula (γ) 3 is -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2, in which M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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.

10. The manufacturing method according to claim 8 or 9, wherein: In the general formula (γ), R 14 It is an aliphatic hydrocarbon group containing one or more carbonyl groups.

11. The manufacturing method according to claim 8 or 9, wherein: In the general formula (γ), R 14 It is an aliphatic hydrocarbon group without a carbonyl group.

12. The production method according to any one of claims 1 to 7, wherein: The hydrocarbon-based surfactant (B) is a surfactant represented by the following general formula: CH3-(CH2) n -AND 5 Wherein, n is an integer from 1 to 2000, Y 5 It is a hydrophilic group.

13. The manufacturing method according to claim 12, wherein: Y 5 is -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM, -B(OM)2 or -OB(OM)2, in which M is H, metal atom, NR 7 4. an imidazolium which may be substituted, a pyridinium which may be substituted, or a phosphonium which may be substituted, R 7 is 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.

14. The production method according to any one of claims 1 to 13, wherein The amount of the fluorine-containing compound (A) is an amount corresponding to 5 ppm to 5000 ppm of the aqueous medium.

15. The production method according to any one of claims 1 to 14, wherein: The fluorine-containing compound (A) and the hydrocarbon-based surfactant (B) are present in the aqueous medium before all the polymerization initiators used in the polymerization step are present.

16. The production method according to any one of claims 1 to 14, wherein: In the polymerization step, when the solid content concentration of the fluorinated elastomer in the aqueous medium is at most 1.0 mass %, the hydrocarbon surfactant (B) is present in the aqueous medium.

17. The production method according to any one of claims 1 to 14, wherein In the polymerization step, the hydrocarbon-based surfactant (B) is present in the aqueous medium before all the polymerization initiators used in the polymerization step are present.

18. The production method according to any one of claims 1 to 14, wherein In the polymerization step, when the solid content concentration of the fluorinated elastomer in the aqueous medium is at most 1.0 mass %, the fluorinated compound (A) is present in the aqueous medium.

19. The production method according to any one of claims 1 to 14, wherein: In the polymerization step, the fluorine-containing compound (A) is present in the aqueous medium before all the polymerization initiators used in the polymerization step are present.

20. The production method according to any one of claims 1 to 19, wherein The emulsion polymerization is carried out in the presence of a polymerization initiator, which is a water-soluble polymerization initiator.

21. The production method according to any one of claims 1 to 20, wherein: The fluoroelastomer contains -CH2- in the main chain.

22. The production method according to any one of claims 1 to 21, wherein The fluoroelastomer comprises vinylidene fluoride units.

23. The production method according to any one of claims 1 to 22, wherein: In the fluorine-containing elastomer, the composition of vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene is (32 to 85) / (10 to 34) / (0 to 34) (mol %).

24. The production method according to any one of claims 1 to 23, wherein The temperature of the emulsion polymerization is 10°C to 120°C.

25. The production method according to any one of claims 1 to 24, wherein: The emulsion polymerization is iodine transfer polymerization or bromine transfer polymerization.

26. The production method according to any one of claims 1 to 25, wherein The redox initiator is a combination of at least one oxidizing agent selected from the group consisting of persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate and bromates and at least one reducing agent selected from the group consisting of sulfites, bisulfites, bromates, diimides, oxalic acid and metal sulfinates.

27. The production method according to any one of claims 1 to 26, wherein: The redox initiator is at least one selected from the group consisting of potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / iron (II) sulfate, ammonium persulfate / sulfite / iron (II) sulfate, ammonium persulfate / sulfite, ammonium persulfate / iron (II) sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / sulfite, bromate / bisulfite, and ammonium persulfate / sodium hydroxymethanesulfinate dihydrate.

28. The production method according to any one of claims 1 to 27, wherein The redox initiator is ammonium persulfate / sodium hydroxymethanesulfinate dihydrate.

29. The production method according to any one of claims 1 to 28, wherein The mass ratio of the fluorine-containing compound (A) to the hydrocarbon-based surfactant (B), namely A / B, is 5 / 95 to 95 / 5.

30. The production method according to any one of claims 1 to 29, wherein: The temperature of the emulsion polymerization is 10° C. to 98° C., and the amount of the hydrocarbon surfactant (B) is an amount corresponding to 5 ppm to 500 ppm of the aqueous medium.

31. The manufacturing method according to claim 30, wherein: The mass ratio of the fluorine-containing compound (A) to the hydrocarbon-based surfactant (B), namely A / B, is 5 / 95 to 70 / 30.

32. The production method according to any one of claims 1 to 31, wherein The emulsion polymerization is carried out in the absence of a fluorinated surfactant.

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