Composition including fluororubber

Abstract

Provided is a composition which comprises a polymer (I) including a unit (I) based on a monomer (I) represented by general formula (I) and a fluororubber, wherein the content of the polymer (I) is 0.0001-1.0 mass% with respect to the fluororubber.　Formula (I): CX1X3=CX2R(-CZ1Z2-A0)m (In the formula, X1 and X3 are each independently F, Cl, H, or CF3, X2 is H, F, an alkyl group, or a fluoroalkyl group, A0 is an anionic group, R is a linking group, Z1 and Z2 are each independently H, F, an alkyl group, or a fluoroalkyl group, and m is an integer of 1 or larger.)

Description

Composition containing fluororubber

[0001] The present disclosure relates to a composition containing a fluororubber.

[0002] Patent Document 1 describes a method for producing a fluoropolymer, which comprises a step of obtaining a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing polymerized units (1) based on a monomer represented by the following general formula (1): CX ２ =CY(-CZ ２ -O-Rf-A) (1) (In the formula, X is the same or different and represents -H or -F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z is the same or different and represents -H, -F, an alkyl group or a fluoroalkyl group. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. A is -COOM, -SO ３ M or -OSO ３ M (M is —H, a metal atom, —NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group, provided that at least one of X, Y, and Z contains a fluorine atom.

[0003] Patent Document 2 describes a method for producing a fluorocopolymer, characterized in that when a fluorocopolymer in an aqueous dispersion of a fluorocopolymer produced by emulsion polymerization in the presence of aqueous ammonia is coagulated to separate the fluorocopolymer, a cationic surfactant and a water-soluble organic solvent are used as the coagulating agent.

[0004] International Publication No. 2019 / 168183 Japanese Patent Application Laid-Open No. 2004-285264

[0005] An object of the present disclosure is to provide a composition containing a polymer containing specific polymerization units and a fluororubber, wherein the content of the polymer containing the specific polymerization units is significantly reduced.

[0006] According to a first aspect of the present disclosure, there is provided a composition comprising a polymer (I) containing polymerized units (I) based on a monomer (I) represented by general formula (I) and a fluororubber, wherein the content of the polymer (I) is 0.0001 to 1.0 mass% relative to the fluororubber. １ X ３ =CX ２ R (-CZ １ Z ２ -A ０ ) ｍ (I) (wherein, X １ and X ３ are each independently F, Cl, H or CF ３ and X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is an anionic group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more.

[0007] According to the present disclosure, it is possible to provide a composition containing a polymer containing specific polymerization units and a fluororubber, in which the content of the polymer containing the specific polymerization units is significantly reduced.

[0008] Before specifically describing the present disclosure, some terms used in the present disclosure will be defined or explained.

[0009] In this disclosure, fluororubber refers to an amorphous fluoropolymer. "Amorphous" means that the magnitude of the melting peak (ΔH) appearing in differential scanning calorimetry (DSC) (heating rate 10°C / min) or differential thermal analysis (DTA) (heating rate 10°C / min) of the fluoropolymer is 4.5 J / g or less. Fluororubber exhibits elastomeric properties through crosslinking. Elastomeric properties refer to the ability of a polymer to be stretched and to retain its original length when the force required to stretch the polymer is no longer applied.

[0010] In the present disclosure, the partially fluorinated rubber is a fluoropolymer that contains fluoromonomer units and has a perfluoromonomer unit content of less than 90 mol% relative to all polymerized units, and has a glass transition temperature of 20°C or less and a melting peak (ΔH) magnitude of 4.5 J / g or less.

[0011] In the present disclosure, perfluororubber (perfluoroelastomer) is a fluoropolymer having a perfluoromonomer unit content of 90 mol% or more, preferably 91 mol% or more, relative to all polymerized units, a glass transition temperature of 20°C or less, a melting peak (ΔH) magnitude of 4.5 J / g or less, and a fluorine atom concentration of 71 mass% or more, preferably 71.5 mass% or more. In the present disclosure, the fluorine atom concentration in the fluoropolymer is determined by calculation of the concentration (mass%) of fluorine atoms in the fluoropolymer from the type and content of each monomer constituting the fluoropolymer.

[0012] In the present disclosure, a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule. The perfluoromonomer may be a monomer containing carbon atoms and fluorine atoms, or a monomer in which some of the fluorine atoms bonded to carbon atoms have been substituted with chlorine atoms, or may contain nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, or silicon atoms in addition to carbon atoms. The perfluoromonomer is preferably a monomer in which all hydrogen atoms have been substituted with fluorine atoms. The perfluoromonomer does not include monomers that provide crosslinking sites.

[0013] The monomer that provides a crosslinking site is a monomer (cure site monomer) having a crosslinkable group that provides a fluoropolymer with a crosslinking site for forming a crosslink with a curing agent.

[0014] In the present disclosure, the content of each monomer constituting the fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0015] In the present disclosure, the term "organic group" refers to a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. Examples of the "organic group" include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, a formyl group, RaO-, RaCO-, and RaSO. ２ -, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO ２ -, and RaNRbSO ２ - (In these formulas, Ra is independently an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents; and Rb is independently H or an alkyl group which may have one or more substituents). As the organic group, an alkyl group which may have one or more substituents is preferred.

[0016] In the present disclosure, the term "substituent" refers to a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamido group, an aromatic sulfonamido group, a heterocyclic sulfonamido group, an amino group, and an aliphatic amino group. groups, aromatic amino groups, heterocyclic amino groups, aliphatic oxycarbonylamino groups, aromatic oxycarbonylamino groups, heterocyclic oxycarbonylamino groups, aliphatic sulfinyl groups, aromatic sulfinyl groups, aliphatic thio groups, aromatic thio groups, hydroxy groups, cyano groups, sulfo groups, carboxy groups, aliphatic oxyamino groups, aromatic oxyamino groups, carbamoylamino groups, sulfamoylamino groups, halogen atoms, sulfamoylcarbamoyl groups, carbamoylsulfamoyl groups, dialiphatic oxyphosphinyl groups, and diaromatic oxyphosphinyl groups.

[0017] The aliphatic group may be saturated or unsaturated and may have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic group include alkyl groups having a total of 1 to 8, preferably 1 to 4, carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, and a carbamoylmethyl group.

[0018] The aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

[0019] The heterocyclic group may have a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the heterocyclic group include 5- or 6-membered heterocycles having a total of 2 to 12, preferably 2 to 10, carbon atoms, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.

[0020] The acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the acyl group include acyl groups having a total of 2 to 8, preferably 2 to 4, carbon atoms, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

[0021] The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the acylamino group include acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and alkylcarbonylamino groups having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0022] The aliphatic oxycarbonyl group may be saturated or unsaturated and may have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic oxycarbonyl group include alkoxycarbonyl groups having a total of 2 to 8, preferably 2 to 4, carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a (t)-butoxycarbonyl group.

[0023] The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, or an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, or an N-phenylcarbamoyl group.

[0024] The aliphatic sulfonyl group may be saturated or unsaturated and may have a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aliphatic sulfonyl group include alkylsulfonyl groups having a total of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methanesulfonyl group.

[0025] The aromatic sulfonyl group may have a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the aromatic sulfonyl group include arylsulfonyl groups having a total of 6 to 10 carbon atoms, such as a benzenesulfonyl group.

[0026] The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

[0027] The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the acylamino group include acylamino groups having a total of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably alkylcarbonylamino groups having a total of 2 to 8 carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0028] The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, or a 2-pyridinesulfonamide group.

[0029] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, an arylsulfamoyl group having 7 to 13 carbon atoms in total, and a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms in total, a dialkylsulfamoyl group having 3 to 6 carbon atoms in total, an arylsulfamoyl group having 6 to 11 carbon atoms in total, and a heterocyclic sulfamoyl group having 2 to 10 carbon atoms in total, such as a sulfamoyl group, a methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, and a 4-pyridine sulfamoyl group.

[0030] The aliphatic oxy group may be saturated or unsaturated and may have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. Examples of the aliphatic oxy group include alkoxy groups having a total of 1 to 8, preferably 1 to 6, carbon atoms, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, and a methoxyethoxy group.

[0031] The aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused with the aryl group, or an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0032] The aliphatic thio group may be saturated or unsaturated and includes alkylthio groups having a total of 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group, a carbamoylmethylthio group, and a t-butylthio group.

[0033] The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 9 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 10 carbon atoms, an arylcarbamoylamino group having a total of 7 to 13 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 12 carbon atoms, preferably a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 7 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 6 carbon atoms, an arylcarbamoylamino group having a total of 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having a total of 3 to 10 carbon atoms, such as a carbamoylamino group, a methylcarbamoylamino group, an N,N-dimethylcarbamoylamino group, a phenylcarbamoylamino group, and a 4-pyridinecarbamoylamino group.

[0034] In this disclosure, ranges expressed by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0035] In this disclosure, the term "at least 1" includes all numbers greater than or equal to 1 (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

[0036] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0037] (Composition) The composition of the present disclosure contains a polymer (I) containing polymerized units (I) based on a monomer (I) represented by general formula (I) and a fluororubber. １ X ３ =CX ２R (-CZ １ Z ２ -A ０ ) ｍ (I) (wherein, X １ and X ３ are each independently F, Cl, H or CF ３ and X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is an anionic group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more.

[0038] Patent Document 1 describes a method for producing a fluoropolymer, which comprises a step of obtaining a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium in the presence of the above-mentioned polymer (1). The composition obtained by using this production method contains a relatively large amount of polymer (1).

[0039] The composition of the present disclosure contains polymer (I) and a fluororubber, and further, the content of polymer (I) is 0.0001 to 1.0 mass% relative to the fluororubber. Since the composition of the present disclosure has a significantly reduced content of polymer (I), the crosslinking reaction proceeds smoothly when the composition of the present disclosure is crosslinked, and the resulting crosslinked product has the excellent physical properties of a fluororubber. For example, by using a composition with a significantly reduced content of polymer (I), the crosslinking time can be shortened, and the compression set of the resulting crosslinked product can be reduced.

[0040] The content of polymer (I) in the composition of the present disclosure is 0.0001 to 1.0% by mass, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and preferably 0.5% by mass or less, more preferably 0.2% by mass or less, relative to the fluororubber. The content of polymer (I) may be less than 0.1% by mass, 0.05% by mass or less, or 0.02% by mass or less, relative to the fluororubber.

[0041] The content of polymer (I) in the composition can be determined by solid-state NMR measurement or melt NMR measurement. When polymer (I) contains a carbonyl group, it can also be determined by a Fourier transform infrared spectrometer. Further, the content of polymer (I) in the composition can be determined by solid-state NMR measurement or melt NMR measurement. Furthermore, the content of polymer (I) can be determined by a Fourier transform infrared spectrometer. Further, the content of polymer (I) in the composition can be determined by a Fourier transform infrared spectrometer. Further, the content of polymer (I) in the composition can be determined by a Fourier transform infrared spectrometer. Measurement methods for each polymer are described in Publication No. 2012 / 082707, WO 2012 / 082703, WO 2012 / 082451, WO 2006 / 135825, WO 2004 / 067588, WO 2009 / 068528, JP 2004-075978, JP 2001-226436, WO 1992 / 017635, WO 2014 / 069165, JP 11-181009, etc. As a method for measuring the content of polymer (I), the measurement methods for each polymer described therein can be used.

[0042] The composition of the present disclosure can be produced by polymerizing a fluoromonomer in an aqueous medium in the presence of polymer (I) to obtain a polymerization dispersion containing a fluororubber, and then subjecting the resulting polymerization dispersion to any of the following treatments: (1) contacting the fluororubber in the polymerization dispersion with an alcohol having 3 to 6 carbon atoms per OH group to coagulate the fluororubber; (2) freezing the polymerization dispersion to coagulate the fluororubber; or (3) contacting the fluororubber in the polymerization dispersion with an extremely limited type of organic solvent to coagulate the fluororubber.

[0043] The content of the polymer (I) in the polymerization dispersion is preferably more than 0.20% by mass, more preferably more than 1.0% by mass, and is preferably 50% by mass or less, more preferably 25% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5.0% by mass or less, based on the fluororubber.

[0044] According to the above-mentioned method for producing the composition, the content of polymer (I) in the polymer dispersion can be reduced to within the above-mentioned numerical range of the content of polymer (I) in the composition.

[0045] Next, the components contained in the composition of the present disclosure and their production methods, as well as the polymerization dispersion containing the polymer (I), a fluororubber, and an aqueous medium used to produce the composition of the present disclosure and its production method will be described in more detail.

[0046] (Polymer (I)) The polymer (I) contained in the composition of the present disclosure contains polymerized units (I) based on the monomer (I) represented by general formula (I). CX １ X ３ =CX ２ R (-CZ １ Z ２ -A ０ ) ｍ (I) (wherein, X １ and X ３ are each independently F, Cl, H or CF ３ and X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is an anionic group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more.

[0047] In the present disclosure, anionic groups include anionic groups such as sulfate groups, carboxylate groups, and acid groups such as —COOH, —COONH ４The anionic group includes a functional group that provides an anionic group such as an acid-base group, such as a sulfate group, a carboxylate group, a phosphate group, a phosphonate group, a sulfonate group, or a -C(CF ３ ) ２ OM (wherein M is —H, a metal atom, —NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0048] In the method for producing the composition, one or more types of monomers can be used as the monomer (I) represented by general formula (I). The polymer (I) can contain polymerization units (I) based on one or more types of monomers as the monomer (I) represented by general formula (I).

[0049] R is a linking group. In the present disclosure, a "linking group" is an (m+1)-valent linking group, and when m is 1, it is a divalent linking group. The linking group may be a single bond and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more. There is no upper limit, but it may be, for example, 100 or less, or 50 or less.

[0050] The linking group may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and may optionally contain one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may optionally contain one or more functional groups selected from the group consisting of ester, amide, sulfonamide, carbonyl, carbonate, urethane, urea, and carbamate. The linking group may not contain carbon atoms but may be a catenary heteroatom such as oxygen, sulfur, or nitrogen.

[0051] m is an integer of 1 or more, preferably 1 or 2, and more preferably 1. When m is an integer of 2 or more, Z １ , Z ２ and A０ may be the same or different. Next, a preferred structure when m is 1 in general formula (I) will be described.

[0052] R is preferably a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.

[0053] When R is a divalent organic group, a hydrogen atom bonded to a carbon atom may be replaced with a halogen atom other than fluorine, such as chlorine, and may or may not contain a double bond. R may be either linear or branched, and may be cyclic or acyclic. R may also contain a functional group (e.g., ester, ether, ketone (keto group), amine, halide, etc.).

[0054] R may also be a non-fluorinated divalent organic group, or a partially fluorinated or perfluorinated divalent organic group.

[0055] R may be, for example, a hydrocarbon group in which no fluorine atoms are bonded to the carbon atoms, a hydrocarbon group in which some of the hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms, or a hydrocarbon group in which all of the hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms, and these may contain an oxygen atom, a double bond, or a functional group.

[0056] R is preferably a hydrocarbon group having 1 to 100 carbon atoms which may contain an ether bond or a keto group, and in the hydrocarbon group, some or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine.

[0057] R is preferably —(CH ２ ) ａ -, - (CF ２ ) ａ -, - (CF ２ ) ａ -O-, -O-(CF ２ ) ａ -, - (CF ２ ) ａ -O-(CF ２ ) ｂ -, -O(CF ２ )ａ -O-(CF ２ ) ｂ -、-(CF ２ ) ａ -[O-(CF ２ ) ｂ ] ｃ -、-O(CF ２ ) ａ -[O-(CF ２ ) ｂ ] ｃ -、-[(CF ２ ) ａ -O] ｂ -[(CF ２ ) ｃ -O] ｄ -、-O[(CF ２ ) ａ -O] ｂ -、-O[(CF ２ ) ａ -O] ｂ -[(CF ２ ) ｃ -O] ｄ -、-O-[CF ２ CF(CF ３ )O] ａ -(CF ２ ) ｂ -、-O-(CF ２ ) ａ -O-[CF(CF ３ )CF ２ O] ｂ -、-O-[CF ２ CF(CF ３ )O] ａ -(CF ２ ) ｂ -O-、-O-[CF ２ CF(CF ３ )O] ａ -(CF ２ ) ｂ -O-[CF(CF ３ )CF ２ O] ｃ -、-[CF ２ CF(CF ３ )O] ａ -、-[CF(CF ３ )CF ２ O] ａ -、-(CF ２ ) ａ-O-[CF(CF ３ )CF ２ O] ａ -, - (CF ２ ) ａ -O-[CF(CF ３ )CF ２ O] ａ -(CF ２ ) ｂ -, -[CF ２ CF (CF ３ )] ａ -CO-(CF ２ ) ｂ - and at least one selected from combinations thereof. In the formula, a, b, c, and d are independently at least 1. a, b, c, and d may independently be 2 or more, 3 or more, 4 or more, 10 or more, or 20 or more. The upper limit of a, b, c, and d is, for example, 100.

[0058] More preferably, R is —O—CF ２ -, -O-CF ２ CF ２ -, -O-CF ２ CF ２ —O—, —O—CF ２ CF ２ CF ２ -, -O-CF ２ CF ２ CF ２ —O—, —O—CF ２ CF (CF ３ ) -O-, -O-CF ２ CF ２ -O-CF(CF ３ )CF ２ —O—, —O—CF ２ CF (CF ３ )-O-CF ２ CF ２ —O— and —O—CF ２ CF (CF ３ )-O-CF ２ - At least one selected from the following.

[0059] R is a group represented by the general formula (r1): -CF ２ -O-(CX ６２ ) ｅ -{O-CF(CF ３ ) ｆ -(O) ｇ - (r1) (wherein, X ６ are each independently H, F or CF ３ wherein e is an integer of 0 to 3, f is an integer of 0 to 3, and g is 0 or 1), and a divalent group represented by the general formula (r2): -CF ２ -O-(CX ７ ２ ) ｅ -(O) ｇ - (r2) (wherein, X ７ are each independently H, F or CF ３ wherein e is an integer of 0 to 3, and g is 0 or 1) is more preferred.

[0060] A specific example of a suitable R is —CF ２ —O—, —CF ２ -O-CF ２ -, -CF ２ -O-CH ２ -, -CF ２ -O-CH ２ CF ２ -, -O-CF ２ -, -O-CF ２ CF ２ -, -O-CF ２ CF ２ CF ２ -, -O-CF ２ CF ２ CF ２ CF ２ -, -O-CF ２ CF (CF ３ )-O-CF ２ -, -O-CF ２ CF (CF ３ )-O-CF ２ CF ２ -, -CF ２ -O-CF ２ CF ２ -, -CF ２ -O-CF ２ CH ２ -, -CF ２ -O-CF ２CF ２ CH ２ -, -CF ２ -O-CF(CF ３ ) -, -CF ２ -O-CF(CF ３ )CF ２ -, -CF ２ -O-CF(CF ３ )CF ２ —O—, —CF ２ -O-CF(CF ３ )CF ２ -O-CF ２ -, -CF ２ -O-CF(CF ３ ) CH ２ Among these, R is preferably a perfluoroalkylene group which may contain an oxygen atom, specifically, —CF ２ —O—, —CF ２ -O-CF ２ -, -O-CF ２ -, -O-CF ２ CF ２ -, -O-CF ２ CF (CF ３ )-O-CF ２ -, -O-CF ２ CF (CF ３ )-O-CF ２ CF ２ -, -CF ２ -O-CF ２ CF ２ -, -CF ２ -O-CF(CF ３ ) -, -CF ２ -O-CF(CF ３ )CF ２ - or -CF ２ -O-CF(CF ３ )CF ２ —O— is preferred.

[0061] -R-CZ of general formula (I) １ Z ２ - is a group represented by the general formula (s1): -CF ２ -O-(CX ６ ２ ) ｅ -{O-CF(CF ３ ) ｆ-(O) ｇ -CZ １ Z ２ - (s1) (wherein, X ６ are each independently H, F or CF ３ wherein e is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, and Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group), and in formula (s1), Z １ and Z ２ is F or CF ３ is more preferred, one of which is F and the other is CF ３ It is more preferable that:

[0062] In addition, in the general formula (I), -R-CZ １ Z ２ - is a group represented by the general formula (s2): -CF ２ -O-(CX ７ ２ ) ｅ -(O) ｇ -CZ １ Z ２ - (s2) (wherein, X ７ are each independently H, F or CF ３ where e is an integer of 0 to 3, g is 0 or 1, and Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group), and in formula (s2), Z １ and Z ２ is F or CF ３ is more preferred, one of which is F and the other is CF ３ It is more preferable that:

[0063] -R-CZ of general formula (I) １ Z ２ - is -CF ２ -O-CF ２ -, -O-CF ２ CF ２ -, -O-CF ２ CF ２ CF ２ -, -O-CF２ CF ２ CF ２ CF ２ -、-O-CF ２ CF(CF ３ )-O-CF ２ -、-O-CF ２ CF(CF ３ )-O-CF ２ CF ２ -、-O-CF ２ CF(CF ３ )-O-CF ２ CF ２ CF ２ -、-CF ２ -O-CF(CF ３ )-、-CF ２ -O-C(CF ３ ) ２ -、-CF ２ -O-CF ２ -CF ２ -、-CF ２ -O-CF ２ -CF(CF ３ )-、-CF ２ -O-CF ２ -C(CF ３ ) ２ -、-CF ２ -O-CF ２ CF ２ -CF ２ -、-CF ２ -O-CF ２ CF ２ -CF(CF ３ )-、-CF ２ -O-CF ２ CF ２ -C(CF ３ ) ２ -、-CF ２ -O-CF(CF ３ )-CF ２ -、-CF ２ -O-CF(CF ３ )-CF(CF ３ )-、-CF ２ -O-CF(CF ３ )-C(CF ３ ) ２ -、-CF ２ -O-CF(CF ３ )CF２ -CF ２ -、-CF ２ -O-CF(CF ３ )CF ２ -CF(CF[[ID=I0]] ３ )-、-CF ２ -O-CF(CF ３ )CF ２ -C(CF ３ ) ２ -、-CF ２ -O-CF(CF ３ )CF ２ -O-CF ２ -、-CF ２ -O-CF(CF ３ )CF ２ -O-CF(CF ３ )-、または、-CF ２ -O-CF(CF ３ )CF ２ -O-C(CF ３ ) ２ -が好ましく、-O-CF ２ CF ２ -、-O-CF ２ CF ２ CF ２ -、-O-CF ２ CF ２ CF ２ CF ２ -、-O-CF ２ CF(CF ３ )-O-CF ２ -、-O-CF ２ CF(CF ３ )-O-CF ２ CF ２ -、-CF ２ -O-CF(CF ３ )-、-CF ２ -O-CF ２ -CF(CF ３ )-、-CF ２ -O-CF ２ CF ２ -CF(CF ３ )-、-CF ２ -O-CF(CF ３ )-CF(CF ３ )-、-CF ２ -O-CF(CF ３ )CF ２-CF (CF ３ ) - or -CF ２ -O-CF(CF ３ )CF ２ -O-CF(CF ３ )- is more preferred, and —O—CF ２ CF ２ -, -O-CF ２ CF (CF ３ )-O-CF ２ CF ２ - is more preferred.

[0064] It is also preferred that the polymer (I) is highly fluorinated. For example, the polymer (I) contains phosphate group moieties (e.g., CH ２ OP (O) (OM) ２ ) and sulfate group moieties (e.g., CH ２ OS (O) ２ anionic groups (A) such as ０ ), it is preferred that 80% or more, 90% or more, 95% or more, or 100% of the C—H bonds in polymer (I) are substituted with C—F bonds.

[0065] The monomer (I) and the polymer (I) contain an anionic group (A ０ ) except for the above, it is also preferable that the compound has a C—F bond and does not have a C—H bond. １ , X ２ , and X ３ is preferably F, and R is a perfluoroalkylene group having one or more carbon atoms, and the perfluoroalkylene group may be either linear or branched, may be cyclic or acyclic, and may contain at least one catenary heteroatom. The number of carbon atoms in the perfluoroalkylene group may be 2 to 20, or may be 4 to 18.

[0066] The monomer (I) and the polymer (I) may be partially fluorinated. That is, the monomer (I) and the polymer (I) may have an anionic group (A ０ ), it is also preferred that the alkyl group has at least one hydrogen atom bonded to a carbon atom and at least one fluorine atom bonded to a carbon atom.

[0067] Anionic group (A ０ ) is -SO ２ M, -SO ３ M, -OSO ３ M, -COOM, -SO ２ NR'CH ２ COOM, -CH ２ OP (O) (OM) ２ , [-CH ２ O] ２ P(O)(OM), -CH ２ CH ２ OP (O) (OM) ２ , [-CH ２ CH ２ O] ２ P(O)(OM), -CH ２ CH ２ OSO ３ M, -P(O)(OM) ２ , -SO ２ NR'CH ２ CH ２ OP (O) (OM) ２ , [-SO ２ NR'CH ２ CH ２ O] ２ P(O)(OM), -CH ２ OSO ３ M, -SO ２ NR'CH ２ CH ２ OSO ３ M, or -C(CF ３ ) ２ Among them, -SO ３ M, -OSO ３ M, -COOM, -P(O)(OM) ２ or -C(CF ３ ) ２ -OM is preferred, -COOM and -SO ３ M, -OSO ３ M, -P(O)(OM) ２ or -C(CF ３ ) ２ OM is more preferred, and —SO ３ M, -COOM or -P(O)(OM) ２ is more preferred, and —SO ３M or -COOM is particularly preferred.

[0068] M is H, a metal atom, or NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0069] The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li.

[0070] M is —H, a metal atom, or NR ７ ４ is preferred, and —H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR ７ ４ is more preferred, and —H, —Na, —K, —Li or NH ４ is more preferred, and —H, —Na, —K or NH ４ is even more preferred, -H, -Na or NH ４ is particularly preferred, and —H or —NH ４ is most preferred.

[0071] In the polymer (I), each polymer unit (I) may have a different anionic group or may have the same anionic group.

[0072] The monomer (I) is preferably a monomer represented by the general formula (Ia). The polymer (I) is preferably a polymer containing a polymerized unit (Ia) based on the monomer represented by the general formula (Ia). CF ２ ═CF—O—Rf ０ -A ０ (Ia) (wherein A ０ is an anionic group, and Rf ０ is a perfluorinated divalent linking group which may be linear or branched, cyclic or acyclic in structure, saturated or unsaturated, substituted or unsubstituted, and which optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0073] The monomer (I) is preferably a monomer represented by the general formula (Ib). The polymer (I) is preferably a polymer containing a polymerized unit (Ib) based on the monomer represented by the general formula (Ib). CH ２ ═CH—O—Rf ０ -A ０ (Ib) (wherein, A ０ is an anionic group, and Rf ０ is a perfluorinated divalent linking group as defined in formula Ia.

[0074] In general formula (I), A ０ is a sulfate group. ０ is, for example, -CH ２ OSO ３ M, -CH ２ CH ２ OSO ３ M or -SO ２ NR'CH ２ CH ２ OSO ３ M, where R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0075] A ０ is a sulfate group, examples of the monomer represented by general formula (I) include CF ２ =CF(OCF ２ CF ２ CH ２ OSO ３ M), CF ２ =CF(O(CF ２ ) ４ CH ２ OSO ３ M), CF ２ =CF(OCF ２ CF (CF ３ ) CH ２ OSO ３ M), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CH ２ OSO ３ M), CH ２ =CH(O(CF２ ) ４ CH ２ OSO ３ M), CF ２ =CF(OCF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OSO ３ M), CH ２ =CH(OCF ２ CF ２ CH ２ OSO ３ M), CF ２ =CF(OCF ２ CF ２ CF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OSO ３ M), CH ２ =CH(OCF ２ CF ２ CF ２ CH ２ OSO ３ In the above formula, M is the same as above.

[0076] In general formula (I), A ０ In one preferred embodiment, A is a sulfonate group. ０ For example, -SO ３ M, where M is the same as above.

[0077] A ０ is a sulfonate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ SO ３ M), CF ２ =CF(O(CF ２ ) ３ SO ３ M), CF ２ =CF(O(CF ２ ) ４ SO ３ M), CF ２ =CF(OCF２ CF (CF ３ ) SO ３ M), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ SO ３ M), CH ２ =CH(OCF ２ CF ２ SO ３ M), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ CF ２ SO ３ M), CH ２ =CH(O(CF ２ ) ４ SO ３ M), CH ２ =CH(O(CF ２ ) ３ SO ３ In the above formula, M is the same as above.

[0078] In general formula (I), A ０ In one preferred embodiment, A is a carboxylate group. ０ Examples of the ２ NR'CH ２ COOM, where R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above. ０ is a carboxylate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ COOM), C.F. ２ =CF(O(CF ２ ) ３ COOM), C.F. ２ =CF(O(CF ２ ) ４ COOM), C.F. ２ =CF(O(CF ２ ) ５ COOM), C.F. ２ =CF(OCF２ CF(CF ３ )(COOM), CF ２ =CF(OCF ２ CF(CF ３ )(OCF ２ )(n is greater than 1), CH ｎ =CH(OCF ２ CF ２ COOM), CH ２ =CH(O(CF ２ )(COOM), CH ２ )(COOM), CH ４ =CH(O(CF ２ )(COOM), CF ２ =CF(OCF ３ CF ２ =CF(OCF ２ CF ２ SO ２ NR'CH ２ COOM), CF ２ =CF(O(CF ２ )(SO ４ NR'CH ２ COOM), CF ２ =CF(OCF ２ CF(CF ２ )(SO ３ NR'CH ２ COOM), CF ２ =CF(OCF ２ CF(CF ２ )(OCF ３ CF ２ SO ２ NR'CH ２ COOM), CH ２ =CH(OCF ２ CF ２ SO ２ NR'CH ２ COOM), CF ２ =CF(OCF ２ CF(CF ２ )(OCF ３ CF ２ CF ２ CF ２ CF ２ SO ２ NR'CH ２ COOM), CH ２ =CH(O(CF ２ )(SO ４ NR'CH２ NR'CH ２ COOM), CH ２ =CH(O(CF ２ ) ３ SO ２ NR'CH ２ In the above formula, R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0079] In general formula (I), A ０ In one preferred embodiment, A is a phosphate group. ０ Examples of the group include -CH ２ OP (O) (OM) ２ , [-CH ２ O] ２ P(O)(OM), -CH ２ CH ２ OP (O) (OM) ２ , [-CH ２ CH ２ O] ２ P(O)(OM), [-SO ２ NR'CH ２ CH ２ O] ２ P(O)(OM) or SO ２ NR'CH ２ CH ２ OP (O) (OM) ２ wherein R' is an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0080] A ０ is a phosphate, the monomer represented by general formula (I) is CF ２ =CF(OCF ２ CF ２ CH ２ OP (O) (OM) ２ ), CF ２ =CF(O(CF ２ ) ４ CH ２ OP (O) (OM) ２ ), CF ２ =CF(OCF ２ CF (CF ３ ) CH ２ OP (O) (OM) ２ ), CF２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ CH ２ OP (O) (OM) ２ ), CF ２ =CF(OCF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OP (O) (OM) ２ ), CF ２ =CF(OCF ２ CF ２ CF ２ CF ２ SO ２ N (CH ３ ) CH ２ CH ２ OP (O) (OM) ２ ), C.H. ２ =CH(OCF ２ CF ２ CH ２ OP (O) (OM) ２ ), C.H. ２ =CH(O(CF ２ ) ４ CH ２ OP (O) (OM) ２ ), C.H. ２ =CH(O(CF ２ ) ３ CH ２ OP (O) (OM) ２ In the above formula, M is the same as above.

[0081] In general formula (I), A ０ In one preferred embodiment, A is a phosphonate group. ０ is a phosphonate group, the monomer represented by general formula (I) is ２ =CF(OCF ２ CF ２ P(O)(OM) ２ ), CF ２ =CF(O(CF ２ ) ４ P(O)(OM) ２ ), CF ２=CF(OCF ２ CF (CF ３ ) P (O) (OM) ２ ), CF ２ =CF(OCF ２ CF (CF ３ ) OCF ２ CF ２ P(O)(OM) ２ ), C.H. ２ =CH(OCF ２ CF ２ P(O)(OM) ２ ), C.H. ２ =CH(O(CF ２ ) ４ P(O)(OM) ２ ), C.H. ２ =CH(O(CF ２ ) ３ P(O)(OM) ２ ) wherein M is the same as above.

[0082] The monomer (I) is preferably a monomer (1) represented by the general formula (1). The polymer (I) is preferably a polymer (1) containing a polymer unit (1) based on the monomer represented by the general formula (1). CX ２ =CY(-CZ ２ -O-Rf-A) (1) (In the formula, X is the same or different and represents -H or F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Z is the same or different and represents -H, -F, an alkyl group or a fluoroalkyl group. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. A is -COOM, -SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is -H, metal atom, -NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.) However, at least one of X, Y, and Z contains a fluorine atom.)

[0083] In the method for producing the composition, the monomer (1) represented by the general formula (1) may be copolymerized with another monomer. The polymer (1) may be a homopolymer of the monomer (1) represented by the general formula (1), or may be a copolymer with another monomer.

[0084] The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0085] In general formula (1), X is —H or F. Both Xs may be —F, or at least one X may be —H. For example, one X may be —F and the other may be —H, or both Xs may be —H.

[0086] In general formula (1), Y is -H, -F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The Y may be -H, -F or CF ３ is preferred, and —F is more preferred.

[0087] In general formula (1), Z's may be the same or different and are -H, -F, an alkyl group, or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The Z's may be -H, -F, or CF ３ is preferred, and —F is more preferred.

[0088] In general formula (1), at least one of X, Y, and Z contains a fluorine atom. For example, X may be —H, and Y and Z may be —F.

[0089] In the general formula (1), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond.

[0090] The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. The number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, particularly preferably 6 or less, and most preferably 3 or less. The fluorine-containing alkylene group includes, for example, —CF ２ -, -CH ２ CF ２ -, -CF ２ CF ２ -, -CF ２ CH ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF ２ CH ２ -, -CF(CF ３ ) -, -CF(CF ３ )CF ２ -, -CF(CF ３ ) CH ２ The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0091] The number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 3 or more. The number of carbon atoms of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, particularly preferably 9 or less, and most preferably 6 or less. The fluorine-containing alkylene group having an ether bond is, for example, a group represented by the general formula: (In the formula, Z １ is F or CF ３ ;Z ２ and Z ３ are H or F; Z ４ is H, F or CF ３p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5).

[0092] Specific examples of the fluorine-containing alkylene group having an ether bond include —CF ２ CF (CF ３ ) OCF ２ -, -CF(CF ３ )CF ２ -O-CF(CF ３ )-,-(CF(CF ３ )CF ２ -O) ｎ -CF (CF ３ )-(wherein n is an integer from 1 to 10), -CF(CF ３ )CF ２ -O-CF(CF ３ ) CH ２ -, -(CF(CF ３ )CF ２ -O) ｎ -CF (CF ３ ) CH ２ - (wherein n is an integer of 1 to 10), -CH ２ CF ２ CF ２ O-CH ２ CF ２ CH ２ -, -CF ２ CF ２ CF ２ O-CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ CH ２ -, -CF ２ CF ２ O-CF ２ -, -CF ２ CF２ O-CF ２ CH ２ The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0093] In the general formula (1), A is -COOM, -SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group).

[0094] R ７ As the group, H or C １－１０ is preferably an organic group of the formula １－４ More preferred are organic groups of the formula: １－４ More preferred are alkyl groups of the formula:

[0095] The metal atom includes alkali metals (Group 1) and alkaline earth metals (Group 2), and is preferably Na, K or Li.

[0096] M is H, a metal atom, or NR ７ ４ is preferred, and H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR ７ ４ is more preferred, and H, Na, K, Li or NH ４ is more preferred, and H, Na, K or NH ４ is even more preferred, H, Na or NH ４ is particularly preferred, and H or NH ４ is most preferred.

[0097] A is -COOM or -SO ３ M is preferred.

[0098] Examples of the monomer represented by the general formula (1) include a monomer represented by the general formula (1a): CX ２ =CFCF ２-O-(CF(CF ３ )CF ２ O) ｎ５ -CF (CF ３ )-A (1a) (wherein each X is the same and represents F or H, n5 represents 0 or an integer of 1 to 10, and A is as defined above).

[0099] In general formula (1a), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, in that particles having a small primary particle size can be obtained.

[0100] In the method for producing the composition, the monomer represented by general formula (1a) may be copolymerized with another monomer, and the polymer (1) may be a homopolymer of the monomer represented by general formula (1a) or a copolymer with another monomer.

[0101] The monomer (1) is preferably a monomer represented by the general formula (1A). The polymerized unit (1) is preferably a polymerized unit (1A) based on a monomer represented by the general formula (1A). CH ２ =CF(-CF ２ —O—Rf-A) (1A) (wherein Rf and A are the same as defined above.)

[0102] In the method for producing the composition, the monomer represented by formula (1A) may be copolymerized with another monomer, and the polymer (1) may be a homopolymer of the monomer represented by formula (1A) or a copolymer with another monomer.

[0103] Specific examples of the monomer represented by formula (1A) include the monomer represented by the general formula:

[0104]

[0105] (In the formula, Z １ is F or CF ３ ;Z ２ and Z ３ are H or F; Z ４ is H, F or CF ３p1+q1+r1 is an integer of 0 to 10; s1 is 0 or 1; t1 is an integer of 0 to 5, provided that Z ３ and Z ４ are both H, then p1+q1+r1+s1 is not 0; A is the same as defined above). More specifically,

[0106]

[0107] Among them,

[0108]

[0109] It is preferable that:

[0110] In the monomer represented by the general formula (1A), A in the formula (1A) is preferably -COOM, and particularly preferably CH ２ =CFCF ２ OCF (CF ３ ) COOM, and CH ２ =CFCF ２ OCF (CF ３ )CF ２ OCF (CF ３ )COOM (wherein M is as defined above), and CH ２ =CFCF ２ OCF (CF ３ ) COOM is more preferred.

[0111] Further, examples of the monomer represented by general formula (1) include a monomer represented by the following formula: CF ２ =CFCF ２ -O-Rf-A (wherein Rf and A are the same as above)

[0112] More specifically, etc.

[0113] The monomer (I) is preferably a monomer (2) represented by the general formula (2). The polymer (I) is preferably a polymer (2) containing a polymer unit (2) based on the monomer represented by the general formula (2). CX ２=CY(-O-Rf-A) (2) (In the formula, X's may be the same or different and each represent -H or F; Y represents -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf represents a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond or a keto group; and A is the same as defined above.)

[0114] In the method for producing the composition, the monomer (2) represented by the general formula (2) may be copolymerized with another monomer. The polymer (2) may be a homopolymer of the monomer represented by the general formula (2) or a copolymer with another monomer.

[0115] In general formula (2), X is —H or F. Both Xs may be —F, or at least one X may be —H. For example, one X may be —F and the other may be —H, or both Xs may be —H.

[0116] In general formula (2), Y is -H, -F, an alkyl group, or a fluorine-containing alkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The fluorine-containing alkyl group preferably has six or fewer carbon atoms, more preferably four or fewer carbon atoms, and even more preferably three or fewer carbon atoms. Y is -H, -F, or -CF ３ is preferred, and —F is more preferred.

[0117] In general formula (2), it is preferable that at least one of X and Y contains a fluorine atom. For example, X may be —H, and Y and Z may be —F.

[0118] In general formula (2), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, or a fluorine-containing alkylene group having a keto group having 2 to 100 carbon atoms. The fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0119] The carbon number of the fluorine-containing alkylene group of Rf is preferably 2 or more, and more preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less. Examples of the fluorine-containing alkylene group include -CF ２ -, -CH ２ CF ２ -, -CF ２ CF ２ -, -CF ２ CH ２ -, -CF ２ CF ２ CH ２ -, -CF(CF ３ ) -, -CF(CF ３ )CF ２ -, -CF(CF ３ ) CH ２ -, -CF ２ CF ２ CF ２ -, CF ２ CF ２ CF ２ CF ２ The fluorine-containing alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0120] 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, even more preferably 12 or less, and particularly preferably 5 or less. The fluorine-containing alkylene group having an ether bond is, for example, a group represented by the general formula: (In the formula, Z １ is F or CF ３ ;Z ２ and Z３ are H or F; Z ４ is H, F or CF ３ p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; and t1 is an integer of 0 to 5).

[0121] Specific examples of the fluorine-containing alkylene group having an ether bond include —CF ２ CF (CF ３ ) OCF ２ -, -CF ２ CF (CF ３ ) OCF ２ CF ２ -, -CF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ -, -CF(CF ３ )CF ２ -O-CF(CF ３ )-,-(CF(CF ３ )CF ２ -O) ｎ -CF (CF ３ )-(wherein n is an integer from 1 to 10), -CF(CF ３ )CF ２ -O-CF(CF ３ ) CH ２ -, -(CF(CF ３ )CF ２ -O) ｎ -CF (CF ３ ) CH ２ - (wherein n is an integer of 1 to 10), -CH ２ CF ２ CF ２ O-CH ２ CF ２ CH ２ -, -CF ２ CF ２ CF ２ O-CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ -, -CF ２ CF ２ CF ２ O-CF２ CF ２ CF ２ -, -CF ２ CF ２ CF ２ O-CF ２ CF ２ CH ２ -, -CF ２ CF ２ O-CF ２ -, -CF ２ CF ２ O-CF ２ CH ２ The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

[0122] The number of carbon atoms in the fluorine-containing alkylene group having a keto group is preferably 3 or more. The number of carbon atoms in the fluorine-containing alkylene group having a keto group is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less.

[0123] Specific examples of the fluorine-containing alkylene group having a keto group include: ２ CF (CF ３ )CO-CF ２ -, -CF ２ CF (CF ３ )CO-CF ２ CF ２ -, -CF ２ CF (CF ３ )CO-CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３ )CO-CF ２ CF ２ CF ２ CF ２ The fluorine-containing alkylene group having a keto group is preferably a perfluoroalkylene group.

[0124] Water may be added to the keto group in the fluorine-containing alkylene group. Therefore, the monomer (2) may be a hydrate. Examples of the fluorine-containing alkylene group in which water is added to the keto group include —CF ２ CF (CF ３ )C(OH)２ -CF ２ -, -CF ２ CF (CF ３ )C(OH) ２ -CF ２ CF ２ -, -CF ２ CF (CF ３ )C(OH) ２ -CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３ )C(OH) ２ -CF ２ CF ２ CF ２ CF ２ --etc.

[0125] The monomer represented by general formula (2) is preferably at least one selected from the group consisting of monomers represented by general formulas (2a), (2b), (2c), (2d), (2e), (2f) and (2g). ２ =CF-O-(CF ２ ) ｎ１ -A (2a) (wherein n1 represents an integer of 1 to 10, and A is the same as defined above) CF ２ =CF-O-(CF ２ C (CF ３ ) F) ｎ２ -A (2b) (wherein n2 represents an integer of 1 to 5, and A is as defined above) CF ２ =CF-O-(CFX １ ) ｎ３ -A (2c) (wherein, X １ is F or CF ３ wherein n3 represents an integer of 1 to 10, and A is as defined above. ２ =CF-O-(CF ２ CFX １ O) ｎ４ -(CF ２ ) ｎ６ -A (2d) (wherein n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and A and X １ is the same as the definition above.) CF ２=CF-O-(CF ２ CF ２ CFX １ O) ｎ５ -CF ２ CF ２ CF ２ -A (2e) (wherein n5 represents an integer of 0 to 10, and A and X １ is the same as the definition above.) CF ２ =CF-O-(CF ２ ) ｎ７ -O-(CF ２ ) ｎ８ -A (2f) (wherein n7 represents an integer of 1 to 10, n8 represents an integer of 1 to 3, and A is as defined above.) CF ２ =CF[OCF ２ CF (CF ３ )] ｎ９ O (CF ２ ) ｎ１０ O[CF(CF ３ )CF ２ O] ｎ１１ CF (CF ３ )-A (2g) (wherein n9 represents an integer of 0 to 5, n10 represents an integer of 1 to 8, and n11 represents an integer of 0 to 5. A is as defined above.)

[0126] In the general formula (2a), n1 is preferably an integer of 5 or less, and more preferably an integer of 2 or less.

[0127] Examples of the monomer represented by general formula (2a) include CF ２ =CF-O-CF ２ COOM, C.F. ２ =CF(OCF ２ CF ２ COOM), C.F. ２ =CF(O(CF ２ ) ３ COOM), C.F. ２ =CF(OCF ２ CF ２ SO ３ M), CF ２ = CFOCF ２ SO ３ M., C.F. ２ = CFOCF ２ CF２ CF ２ SO ３ M (wherein M is as defined above).

[0128] In general formula (2b), n2 is preferably an integer of 3 or less, from the viewpoint of the dispersion stability of the resulting composition.

[0129] In the general formula (2c), n3 is preferably an integer of 5 or less from the viewpoint of water solubility, A is preferably -COOM, and M is preferably H, Na, or NH ４ It is preferable that:

[0130] In general formula (2d), X １ In terms of dispersion stability of the composition, -CF ３ n4 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is H, Na, or NH ４ It is preferable that:

[0131] Examples of the monomer represented by general formula (2d) include CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ COOM, C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ COOM, C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CF ２ COOM, C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ SO ３ M., C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ SO ３ M., C.F. ２ = CFOCF ２ CF (CF３ ) OCF ２ CF ２ CF ２ SO ３ M (wherein M is H, NH ４ or an alkali metal.

[0132] In the general formula (2e), n5 is preferably an integer of 5 or less from the viewpoint of water solubility, A is preferably -COOM, and M is preferably H or NH ４ It is preferable that:

[0133] Examples of the monomer represented by general formula (2e) include CF ２ = CFOCF ２ CF ２ CF ２ COOM (wherein M is H, Na, NH ４ or an alkali metal.

[0134] In the general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, and A is -COOM or -SO ３ M is preferred, and -COOM is more preferred. M is H, Na, K or NH ４ It is preferable that:

[0135] Examples of the monomer represented by general formula (2f) include CF ２ =CF-O-(CF ２ ) ３ -O-CF ２ -COOM (wherein M is H, NH ４ or an alkali metal.

[0136] In the general formula (2g), n9 is preferably an integer of 3 or less in terms of water solubility, n10 is preferably an integer of 3 or less, n11 is preferably an integer of 3 or less, and A is -COOM or -SO ３ M is preferred, and -COOM is more preferred. M is H, Na, K or NH ４ It is preferable that:

[0137] Examples of the monomer represented by general formula (2g) include CF ２= CFO (CF ２ ) ２ OCF (CF ３ ) COOM, C.F. ２ = CFOCF ２ CF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM, C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ OCF (CF ３ ) COOM, C.F. ２ =CF[OCF ２ CF (CF ３ )] ２ O (CF ２ ) ２ O[CF(CF ３ )CF ２ O]CF(CF ３ ) COOM, C.F. ２ =CF[OCF ２ CF (CF ３ )] ３ O (CF ２ ) ２ O[CF(CF ３ )CF ２ O] ３ CF (CF ３ ) COOM (wherein M is H, NH ４ or an alkali metal.

[0138] The monomer (I) is preferably a monomer (3) represented by the general formula (3). The polymer (I) is preferably a polymer (3) containing a polymer unit (3) based on the monomer represented by the general formula (3). CX ２ =CY(-Rf-A) (3) (In the formula, X is the same or different and represents -H or F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond; and A is the same as defined above.)

[0139] In the method for producing the composition, the monomer (3) represented by the general formula (3) may be copolymerized with another monomer. The polymer (3) may be a homopolymer of the monomer represented by the general formula (3) or a copolymer with another monomer.

[0140] The fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond is an alkylene group that does not contain a structure in which an oxygen atom is at the terminal and that contains an ether bond between carbon atoms.

[0141] In general formula (3), Rf is preferably a fluorine-containing alkylene group having 1 to 40 carbon atoms. In general formula (3), at least one of X and Y preferably contains a fluorine atom.

[0142] The monomer represented by the general formula (3) is represented by the general formula (3a): CF ２ =CF-(CF ２ ) ｎ１ -A (3a) (wherein n1 represents an integer of 1 to 10, and A is as defined above), and a monomer represented by the general formula (3b): CF ２ =CF-(CF ２ C (CF ３ ) F) ｎ２ -A (3b) (wherein n2 represents an integer of 1 to 5, and A is as defined above) is preferred.

[0143] In the general formula (3a) and the general formula (3b), A is —SO ３ M or COOM is preferred, where M is H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium. ７ represents H or an organic group.

[0144] In the general formula (3a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. A is preferably -COOM, and M is preferably H or NH. ４ It is preferable that:

[0145] Examples of the monomer represented by general formula (3a) include CF ２ =CFCF ２ COOM (wherein M is as defined above).

[0146] In the general formula (3b), n2 is preferably an integer of 3 or less from the viewpoint of dispersion stability of the resulting composition, A is preferably -COOM, and M is preferably H or NH ４ It is preferable that:

[0147] Next, a preferred structure when m in general formula (I) is an integer of 2 or more will be described.

[0148] It is also preferred that the monomer (I) is at least one selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). It is also preferred that the polymer (I) is a polymer (4) containing polymerization units (4) based on at least one monomer selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). CF ２ =CF-CF ２ -O-Q Ｆ１ -CF(-Q Ｆ２ -CZ １ Z ２ -A) ２ (4a) (wherein, Z １ , Z ２ and A is the same as defined above, Q Ｆ１ and Q Ｆ２ are the same or different and are a single bond, a fluorine-containing alkylene group which may contain an ether bond between carbon atoms, or a fluorine-containing oxyalkylene group which may contain an ether bond between carbon atoms. ２ =CF-O-Q Ｆ１ -CF(-Q Ｆ２ -CZ １ Z ２ -A) ２ (4b) (wherein, Z １ , Z ２ , A, Q Ｆ１ and Q Ｆ２ is the same as above)

[0149] The monomers represented by general formula (4a) and general formula (4b) include: etc.

[0150] The monomer (I) is preferably at least one selected from the group consisting of the monomer (1), the monomer (2), and the monomer (3), and more preferably the monomer (2). The polymer (I) is preferably at least one selected from the group consisting of the polymer (1), the polymer (2), and the polymer (3), and more preferably the polymer (2).

[0151] In the method for producing the composition, the monomer (I) may be copolymerized with another monomer. The polymer (I) may be a homopolymer consisting of only the polymerized unit (I), or may be a copolymer containing the polymerized unit (I) and a polymerized unit based on another monomer copolymerizable with the monomer represented by the general formula (I). From the viewpoint of solubility in an aqueous medium, a homopolymer consisting of only the polymerized unit (I) is preferred. The polymerized units (I) may be the same or different in each occurrence, and the polymer (I) may contain polymerized units (I) based on two or more different monomers represented by the general formula (I).

[0152] The other monomers include those represented by the general formula CFR=CR ２ (wherein R is independently H, F or a perfluoroalkyl group having 1 to 4 carbon atoms) is preferred. As the other monomer, a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms is preferred. As the other monomer, for example, CF ２ =CF ２ , C.F. ２ = CFCl, CH ２ =CF ２ , CFH=CH ２ , CFH=CF ２ , C.F. ２ =CFCF ３ , C.H. ２ =CFCF ３ , C.H. ２ = CHCF ３ , CHF=CHCF ３ (E form), CHF=CHCF ３ Among them, tetrafluoroethylene (CF２ =CF ２ ), chlorotrifluoroethylene (CF ２ =CFCl) and vinylidene fluoride (CH ２ =CF ２ ), and more preferably at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride. Therefore, the polymerized units based on the other monomer are preferably polymerized units based on tetrafluoroethylene. The polymerized units based on the other monomer may be the same or different in each occurrence, and polymer (I) may contain polymerized units based on two or more different other monomers.

[0153] The other monomers also include those represented by the general formula (n1-2):

[0154]

[0155] (In the formula, X １ , X ２ are the same or different and are H or F; X ３ are H, F, Cl, CH ３ or CF ３ ;X ４ , X ５ are the same or different and are H or F; a and c are the same or different and are 0 or 1. ３ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond).

[0156] Specifically, CH ２ =CFCF ２ -O-Rf ３ , C.F. ２ ═CF—O—Rf ３ , C.F. ２ =CFCF ２ -O-Rf ３ , C.F. ２ =CF-Rf ３ , C.H. ２ =CH-Rf ３ , C.H. ２ ═CH—O—Rf ３ (wherein, Rf ３is the same as the above formula (n1-2).

[0157] Examples of the other monomer include a monomer of the formula (n2-1):

[0158]

[0159] (In the formula, X ９ is H, F or CH ３ ; Rf ４ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond). ４ The base is

[0160]

[0161] (wherein d3 is an integer of 1 to 4; e3 is an integer of 1 to 10).

[0162] Examples of the other monomer include a monomer represented by formula (n2-2): CH ２ =CHO-Rf ５ (n2-2) (wherein, Rf ５ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond), and

[0163] Specific examples of the monomer of general formula (n2-2) include:

[0164]

[0165] (wherein e6 is an integer of 1 to 10) are preferred.

[0166] More specifically,

[0167]

[0168] Examples include:

[0169] Others include those represented by the general formula (n2-3): CH ２ =CHCH ２ O-Rf ６ (n2-3) (wherein, Rf ６is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and an ether bond), a fluorine-containing allyl ether represented by the general formula (n2-4): CH ２ =CH-Rf ７ (n2-4) (wherein, Rf ７ is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and having an ether bond), and the like.

[0170] Specific examples of the monomers represented by general formulas (n2-3) and (n2-4) include:

[0171]

[0172] Examples of such monomers include:

[0173] The polymer (I) usually has a terminal group. The terminal group is a terminal group generated during polymerization, and typical terminal groups are independently selected from hydrogen, iodine, bromine, linear or branched alkyl groups, and linear or branched fluoroalkyl groups, and may optionally contain at least one catenary heteroatom. The alkyl group or fluoroalkyl group preferably has 1 to 20 carbon atoms. These terminal groups are generally generated from the initiator or chain transfer agent used in forming the polymer (I) or during the chain transfer reaction.

[0174] In the polymer (I), the content of the polymerized units (I) relative to the total polymerized units is, in order of preference, 1.0 mol% or more, 3.0 mol% or more, 5.0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, and 90 mol% or more. The content of the polymerized units (I) is particularly preferably substantially 100 mol%, and the polymer (I) is most preferably composed only of the polymerized units (I).

[0175] In the polymer (I), the content of polymerization units based on other monomers copolymerizable with the monomer represented by general formula (I) is, in order of preference, 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, and 10 mol% or less, based on all polymerization units. It is particularly preferable that the content of polymerization units based on other monomers copolymerizable with the monomer represented by general formula (I) is substantially 0 mol%, and it is most preferable that the polymer (I) does not contain polymerization units based on other monomers.

[0176] The number average molecular weight of the polymer (I) is 0.1 × 10 ４ More than 0.2 × 10 ４ More preferably, 0.3 × 10 ４ More preferably, 0.4 × 10 ４ More preferably, 0.5 × 10 ４ More preferably, 1.0 x 10 ４ More preferably, 3.0 × 10 ４ More particularly, 3.1 × 10 ４ More than 75.0×10 is most preferable. ４ Preferably, 50.0 x 10 ４ More preferably, 40.0 x 10 ４ More preferably, 30.0 x 10 ４ The following is particularly preferred: 20.0 x 10 ４ The following are particularly preferred. The number average molecular weight and weight average molecular weight are values ​​calculated by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard. When measurement by GPC is not possible, the number average molecular weight of polymer (I) can be determined from the correlation between the number average molecular weight calculated from the number of terminal groups obtained by NMR, FT-IR, etc. and the melt flow rate. The melt flow rate can be measured in accordance with JIS K 7210.

[0177] The lower limit of the weight average molecular weight of the polymer (I) is, in order of preference, 0.2 × 10 ４ That's it, 0.4 x 10４ That's it, 0.6 x 10 ４ That's it, 0.8 x 10 ４ That's it, 1.0 x 10 ４ That's it, 2.0 x 10 ４ That's it, 5.0 x 10 ４ That's it, 10.0 x 10 ４ That's it, 15.0 x 10 ４ That's it, 20.0 x 10 ４ That's it, 25.0 x 10 ４ The upper limit of the weight average molecular weight of the polymer (I) is preferably 150.0×10 ４ Below, 100.0 x 10 ４ Below, 60.0 x 10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ The following is the result.

[0178] The polymer (I) preferably has an ion exchange ratio (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the polymer backbone relative to the ionic group. ２ F) is not considered an ionizable group for purposes of determining IXR.

[0179] IXR is preferably 0.5 or more, more preferably 1 or more, even more preferably 3 or more, even more preferably 4 or more, particularly preferably 5 or more, and particularly preferably 8 or more. IXR is more preferably 43 or less, more preferably 33 or less, and particularly preferably 23 or less.

[0180] The ion exchange capacity of the polymer (I) is, in order of preference, 0.80 meq / g or more, 1.50 meq / g or more, 1.75 meq / g or more, 2.00 meq / g or more, 2.20 meq / g or more, more than 2.20 meq / g, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, and 3.50 meq / g or more. The ion exchange capacity is the content of ionic groups (anionic groups) in the polymer (I) and is calculated from the composition of the polymer (I).

[0181] In polymer (I), the ionic (anionic) groups are typically distributed along the polymer backbone. The polymer (I) comprises a polymer backbone with recurring side chains attached to the backbone, which preferably carry ionic groups.

[0182] Preferably, polymer (I) comprises ionizable groups having a pKa of less than 10, more preferably less than 7. The ionizable groups of polymer (I) are preferably selected from the group consisting of sulfonate, carboxylate, phosphonate, and phosphate.

[0183] The terms "sulfonate, carboxylate, phosphonate, and phosphate" are intended to refer to the respective salts or the respective acids capable of forming salts. When salts are used, the salts are preferably alkali metal or ammonium salts. Preferred ionic groups are carboxylate and sulfonate groups.

[0184] The polymer (I) is preferably water-soluble. Water-soluble means the property of being easily dissolved or dispersed in an aqueous medium. The particle size of the water-soluble polymer (I) cannot be measured by dynamic light scattering (DLS), for example, or the particle size is 10 nm or less.

[0185] The viscosity of an aqueous solution of polymer (I) is preferably 5.0 mPa.s or more, more preferably 8.0 mPa.s or more, even more preferably 10.0 mPa.s or more, particularly preferably 12.0 mPa.s or more, and most preferably 14.0 mPa.s or more, and is preferably 100.0 mPa.s or less, more preferably 50.0 mPa.s or less, even more preferably 25.0 mPa.s or less, and especially preferably 20.0 mPa.s or less.

[0186] The viscosity of the aqueous solution of polymer (I) can be determined by adjusting the content of polymer (I) in the aqueous solution to 33 mass % based on the aqueous solution, and measuring the viscosity of the obtained aqueous solution at 20°C using a tuning fork vibro viscometer (model number: SV-10) manufactured by A&D Co., Ltd.

[0187] The critical micelle concentration (CMC) of the polymer (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less.

[0188] The critical micelle concentration of the polymer (I) can be determined by measuring the surface tension, for example, using a surface tensiometer CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.

[0189] The acid value of the polymer (I) is preferably 60 or more, more preferably 90 or more, even more preferably 120 or more, particularly preferably 150 or more, and most preferably 180 or more. The upper limit is not particularly limited, but is preferably 300 or less.

[0190] The acid value of the polymer (I) is determined by the amount of anionic groups other than the acid functional groups, such as —COOM and —SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ When the compound has a group (H or an organic group), these groups can be converted into acid groups and then measured by acid-base titration.

[0191] The polymer (I) is a polymer (11) of a monomer (11) represented by general formula (11), in which the content of polymerized units (11) based on the monomer (11) is 50 mol% or more based on all polymerized units constituting the polymer (11), and the weight average molecular weight (Mw) is 38.0 × 10 ４ Polymer (11) having the above formula can also be used. Polymer (11) is a novel polymer. ２ =CY-CF ２ -O-Rf-A (wherein X and Y are independently H, F, CH ３ or CF３ and at least one of X and Y is F. Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond. A is -COOM, -SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0192] In the general formula (11), X and Y are independently H, F, CH ３ or CF ３ and at least one of X and Y is F. X is preferably H or F, and more preferably H. Y is preferably H or F, and more preferably F.

[0193] Rf and A in the general formula (11) are the same as Rf and A in the general formula (1) representing the monomer constituting the polymer (1).

[0194] The polymer (11) may be a homopolymer consisting of only polymerized units (11) based on the monomer (11), or may be a copolymer containing polymerized units (11) and polymerized units based on other monomers copolymerizable with the monomer (11). The other monomers are as described above. The polymerized units (11) may be the same or different in each occurrence, and the polymer (11) may contain polymerized units (11) based on two or more different monomers represented by the general formula (11).

[0195] The content of the polymerized units (11) in the polymer (11) is, in order of decreasing preference, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and 99 mol% or more of all the polymerized units constituting the polymer (11). The content of the polymerized units (11) is particularly preferably substantially 100 mol%, and the polymer (11) most preferably consists solely of the polymerized units (11).

[0196] In polymer (11), the content of polymerized units based on other monomers copolymerizable with monomer (11) is, in order of preference, 99.0 mol% or less, 97.0 mol% or less, 95.0 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, and 50 mol% or less, based on all polymerized units constituting polymer (11). It is particularly preferred that the content of polymerized units based on other monomers copolymerizable with monomer (11) is substantially 0 mol%, and it is most preferred that polymer (11) does not contain polymerized units based on other monomers.

[0197] The lower limit of the weight average molecular weight of the polymer (11) is, in order of preference, 38.0 × 10 ４ That's it, 40.0 x 10 ４ The upper limit of the weight average molecular weight of the polymer (11) is, in order of preference, 150.0×10 ４ Below, 100.0 x 10 ４ Below, 60.0 x 10 ４ is.

[0198] The lower limit of the number average molecular weight of the polymer (11) is preferably 5.0 × 10 ４ , 8.0 × 10 ４ , 10.0 × 10 ４ That's it, 12.0 x 10 ４ The upper limit of the number average molecular weight of the polymer (11) is, in order of preference, 75.0 × 10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ Below, 30.0 x 10 ４ The following is the result.

[0199] The polymer (I) is a polymer (12) of a monomer (12) represented by general formula (12), in which the content of polymerized units (12) based on the monomer (12) is 50 mol% or more based on all polymerized units constituting the polymer (12), and the weight average molecular weight (Mw) is 1.4 × 10 ４ Polymer (12) having the above formula can also be used. Polymer (12) is a novel polymer. ２ ═CX—O—Rf-A (wherein X is independently F or CF ３ Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond or a keto group. A is -COOM, -SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is -H, metal atom, -NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0200] In the general formula (12), X is independently F or CF ３ Preferably, at least one X is F, and more preferably, all Xs are F.

[0201] Rf and A in the general formula (12) are the same as Rf and A in the general formula (2) representing the monomer constituting the polymer (2).

[0202] The polymer (12) may be a homopolymer consisting of only polymerized units (12) based on the monomer (12), or may be a copolymer containing polymerized units (12) and polymerized units based on other monomers copolymerizable with the monomer (12). The other monomers are as described above. The polymerized units (12) may be the same or different in each occurrence, and the polymer (12) may contain polymerized units (12) based on two or more different monomers represented by the general formula (12).

[0203] The content of the polymerized units (12) in the polymer (12) is, in order of preference, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and 99 mol% or more, based on all the polymerized units constituting the polymer (12). The content of the polymerized units (12) is particularly preferably substantially 100 mol%, and the polymer (12) most preferably consists solely of the polymerized units (12).

[0204] In the polymer (12), the content of polymerized units based on other monomers copolymerizable with the monomer (12) is, in order of decreasing preference, 50 mol % or less, 40 mol % or less, 30 mol % or less, 20 mol % or less, 10 mol % or less, and 1 mol % or less, based on all polymerized units constituting the polymer (12). It is particularly preferred that the content of polymerized units based on other monomers copolymerizable with the monomer (12) is substantially 0 mol %, and it is most preferred that the polymer (12) does not contain any polymerized units based on other monomers.

[0205] The lower limit of the weight average molecular weight (Mw) of the polymer (12) is, in order of preference, 1.4 × 10 ４ That's it, 1.7 x 10 ４ That's it, 1.9 x 10 ４ That's it, 2.1 x 10 ４ That's it, 2.3 x 10 ４ That's it, 2.7 x 10 ４ That's it, 3.1 x 10 ４ That's it, 3.5 x 10 ４ That's it, 3.9 x 10 ４ That's it, 4.3 x 10 ４ That's it, 4.7 x 10 ４ That's it, 5.1 x 10 ４ The upper limit of the weight average molecular weight (Mw) of the polymer (12) is, in order of preference, 150.0×10 ４ Below, 100.0 x 10 ４ Below, 60.0 x 10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ The following is the result.

[0206] The lower limit of the number average molecular weight (Mn) of the polymer (12) is, in order of preference, 0.7 × 10４ That's it, 0.9 x 10 ４ That's it, 1.0 x 10 ４ That's it, 1.2 x 10 ４ That's it, 1.4 x 10 ４ That's it, 1.6 x 10 ４ That's it, 1.8 x 10 ４ The upper limit of the number average molecular weight (Mn) of the polymer (12) is, in order of preference, 75.0×10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ Below, 30.0 x 10 ４ Below, 20.0 x 10 ４ The following is the result.

[0207] The molecular weight distribution (Mw / Mn) of the polymer (12) is preferably 3.0 or less, more preferably 2.4 or less, even more preferably 2.2 or less, particularly preferably 2.0 or less, and most preferably 1.9 or less.

[0208] When the polymer (12) contains the polymerized units (12) and polymerized units based on other monomers copolymerizable with the monomer (12), the content of the polymerized units (12) based on the monomer (12) is preferably 40 to 60 mol %, more preferably 45 to 55 mol %, based on all the polymerized units constituting the polymer (12), and the content of the polymerized units based on other monomers is preferably 60 to 40 mol %, more preferably 55 to 45 mol %, based on all the polymerized units constituting the polymer (12). Such a configuration is achieved when the polymerized units based on other monomers copolymerizable with the monomer (12) are represented by the general formula CFR=CR ２ It is particularly preferred that the polymerized units (M) are based on a monomer represented by the following formula:

[0209] When the polymer (12) contains the polymerized units (12) and polymerized units based on other monomers copolymerizable with the monomer (12), the alternation ratio of the polymerized units (12) and the polymerized units based on other monomers copolymerizable with the monomer (12) is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more. The alternation ratio may be, for example, 40 to 99%. Such a configuration is achieved when the polymerized units based on other monomers copolymerizable with the monomer (12) are represented by the general formula CFR=CR ２ It is particularly preferred that the polymerized units (M) are based on a monomer represented by the following formula:

[0210] The alternation ratio of the polymerized unit (12) and the polymerized unit based on another monomer copolymerizable with the monomer (12) in the polymer (12) is １９ It can be determined by F-NMR analysis.

[0211] The polymer (I) can be produced by a conventionally known method except for using the above-mentioned monomers.

[0212] As the polymer (I), a polymer (13) of a monomer (13) represented by general formula (13) can also be used, in which the content of polymerized units (13) based on the monomer (13) is 50 mass % or more based on the total polymerized units constituting the polymer (13). The polymer (13) is a novel polymer. General formula (13): CX ２ =CX-O-Rf-SO ３ M (wherein X is independently F or CF ３ wherein Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond or a keto group; M is —H, a metal atom, —NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0213] In the general formula (13), X is independently F or CF ３ Preferably, at least one X is F, and more preferably, all Xs are F.

[0214] Rf and M in the general formula (13) are the same as Rf and A in the general formula (2) representing the monomer constituting the polymer (2).

[0215] The polymer (13) may be a homopolymer consisting of only polymerized units (13) based on the monomer (13), or may be a copolymer containing polymerized units (13) and polymerized units based on other monomers copolymerizable with the monomer (13). The other monomers are as described above. The polymerized units (13) may be the same or different in each occurrence, and the polymer (13) may contain polymerized units (13) based on two or more different monomers represented by the general formula (13).

[0216] The polymer (13) has a content of polymerized units (13) based on the monomer (13) of 50% by mass or more relative to all polymerized units constituting the polymer (13). The content of polymerized units (13) in the polymer (13) relative to all polymerized units constituting the polymer (13) is, in order of preference, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, and 99% by mass or more. It is particularly preferable that the content of polymerized units (13) is substantially 100% by mass, and it is most preferable that the polymer (13) consists solely of polymerized units (13).

[0217] In polymer (13), the content of polymerized units based on other monomers copolymerizable with monomer (13) is, in order of decreasing preference, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, and 1% by mass or less, based on all polymerized units constituting polymer (13). It is particularly preferable that the content of polymerized units based on other monomers copolymerizable with monomer (13) is substantially 0% by mass, and it is most preferable that polymer (13) does not contain polymerized units based on other monomers.

[0218] The lower limit of the number average molecular weight of the polymer (13) is, in order of preference, 0.3 × 10 ４That's it, 0.4 x 10 ４ That's it, 0.5 x 10 ４ That's it, 0.7 x 10 ４ That's it, 0.8 x 10 ４ That's it, 1.0 x 10 ４ That's it, 1.2 x 10 ４ That's it, 1.4 x 10 ４ , 1.6 × 10 ４ That's it, 1.8 x 10 ４ That's it, 2.0 x 10 ４ That's it, 3.0 x 10 ４ The upper limit of the number average molecular weight of the polymer (13) is, in order of preference, 75.0 × 10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ Below, 30.0 x 10 ４ Below, 20.0 x 10 ４ The following is the result.

[0219] The lower limit of the weight average molecular weight of the polymer (13) is, in order of preference, 0.4×10 ４ That's it, 0.5 x 10 ４ That's it, 0.6 x 10 ４ That's it, 0.8 x 10 ４ That's it, 1.0 x 10 ４ That's it, 1.2 x 10 ４ That's it, 1.4 x 10 ４ That's it, 1.7 x 10 ４ That's it, 1.9 x 10 ４ That's it, 2.1 x 10 ４ That's it, 2.3 x 10 ４ That's it, 2.7 x 10 ４ That's it, 3.1 x 10 ４ That's it, 3.5 x 10 ４ That's it, 3.9 x 10 ４ That's it, 4.3 x 10 ４ That's it, 4.7 x 10 ４ That's it, 5.1 x 10 ４ That's it, 10.0 x 10 ４ That's it, 15.0 x 10 ４ That's it, 20.0 x 10 ４ That's it, 25.0 x 10 ４ The upper limit of the weight average molecular weight of the polymer (13) is, in order of preference, 150.0 × 10 ４ Below, 100.0 x 10４ Below, 60.0 x 10 ４ Below, 50.0 x 10 ４ Below, 40.0 x 10 ４ The following is the result.

[0220] The molecular weight distribution (Mw / Mn) of the polymer (13) is preferably 3.0 or less, 2.4 or less, 2.2 or less, 2.0 or less, 1.9 or less, 1.7 or less, 1.5 or less, 1.4 or less, and 1.3 or less.

[0221] Among the polymers (I), the polymer (11) is a novel polymer, and can be produced by a production method (11) in which a polymer (11) of the monomer (11) is produced by polymerizing the monomer (11) represented by the general formula (11) in an aqueous medium, and the oxygen concentration in the polymerization reaction system is maintained at 500 ppm by volume or less.

[0222] In the production method (11), the oxygen concentration in the polymerization reaction system is 500 ppm by volume or less. In the production method (11), the oxygen concentration in the reaction system is maintained at 500 ppm by volume or less throughout the entire polymerization period of the monomer (11). The oxygen concentration in the reaction system is preferably 350 ppm by volume or less, more preferably 300 ppm by volume or less, even more preferably 100 ppm by volume or less, and particularly preferably 50 ppm by volume or less. The oxygen concentration in the reaction system is usually 0.01 ppm by volume or more.

[0223] In the production method (11), the polymerization temperature of the monomer (11) is preferably 59°C or lower, more preferably 57°C or lower, even more preferably 55°C or lower, and particularly preferably 53°C or lower, because a polymer (11) having a higher molecular weight can be easily produced. The polymerization temperature is preferably 20°C or higher, more preferably 25°C or higher, even more preferably 30°C or higher, and particularly preferably 35°C or higher.

[0224] In the production method (11), the monomer (11) may be copolymerized with the other monomers described above.

[0225] In the production method (11), the polymerization pressure is usually from atmospheric pressure to 10 MPaG, and is appropriately determined depending on the type of monomer used, the molecular weight of the target polymer, and the reaction rate.

[0226] In the production method (11), the polymerization time is usually 1 to 200 hours, and may be 5 to 100 hours.

[0227] Among the polymers (I), the polymer (12) is a novel polymer, and can be produced by a production method (12) for producing a polymer (12) from the monomer (12) by polymerizing the monomer (12) represented by the general formula (12) in an aqueous medium, in which the oxygen concentration in the polymerization reaction system is maintained at 1,500 ppm by volume or less.

[0228] In the production method (12), the oxygen concentration in the polymerization reaction system is 1500 ppm by volume or less. In the production method (12), the oxygen concentration in the reaction system is maintained at 1500 ppm by volume or less throughout the entire polymerization period of the monomer (12). The oxygen concentration in the reaction system is preferably 500 ppm by volume or less, more preferably 100 ppm by volume or less, and even more preferably 50 ppm by volume or less. In addition, the oxygen concentration in the reaction system is usually 0.01 ppm by volume or more.

[0229] Among the polymers (I), the polymer (13) is a novel polymer, and can be produced by a method (13) for producing a polymer (13) by polymerizing a monomer (13) represented by general formula (13) in an aqueous medium to produce a polymer (13) of the monomer (13).

[0230] In the production method (13), the oxygen concentration in the polymerization reaction system is preferably 1500 volume ppm or less, more preferably 500 volume ppm or less, even more preferably 100 volume ppm or less, and particularly preferably 50 volume ppm or less. The oxygen concentration in the reaction system is usually 0.01 volume ppm or more. In the above production method, it is preferred that the oxygen concentration in the reaction system be maintained within the above range throughout the entire polymerization period of the monomer (13).

[0231] In the production method (12) and the production method (13), the polymerization temperature of the monomer (12) and the monomer (13) is preferably 70°C or lower, more preferably 65°C or lower, even more preferably 60°C or lower, particularly preferably 55°C or lower, even more preferably 50°C or lower, particularly preferably 45°C or lower, most preferably 40°C or lower, preferably 10°C or higher, more preferably 15°C or higher, and even more preferably 20°C or higher, since this facilitates the production of polymers (12) and (13) having higher molecular weights.

[0232] In the production method (12) and the production method (13), the monomer (12) or the monomer (13) may be copolymerized with the other monomers described above.

[0233] In the production methods (12) and (13), the polymerization pressure is usually atmospheric pressure to 10 MPaG. The polymerization pressure is appropriately determined depending on the type of monomer used, the molecular weight of the target polymer, and the reaction rate.

[0234] In the production methods (12) and (13), the polymerization time is usually 1 to 200 hours, and may be 5 to 100 hours.

[0235] In the production methods (11) to (13), the oxygen concentration in the polymerization reaction system can be controlled, for example, by flowing an inert gas such as nitrogen or argon, or, when a gaseous monomer is used, the gaseous monomer, through the liquid or gas phase in the reactor. The oxygen concentration in the polymerization reaction system can be determined by measuring and analyzing the gas coming out of the exhaust gas line of the polymerization system with a low-concentration oxygen analyzer.

[0236] In the production methods (11) to (13), the aqueous medium is a reaction medium for polymerization and refers to 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 fluorine-free organic solvent such as an alcohol, ether, or ketone, and / or a fluorine-containing organic solvent having a boiling point of 40° C. or lower. Water is preferred as the aqueous medium.

[0237] In the production methods (11) to (13), the polymerization of the monomers can be carried out in the presence of a polymerization initiator. The polymerization initiator is not particularly limited as long as it can generate radicals within the above-mentioned polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, the polymerization can also be initiated as a redox reaction in combination with a reducing agent or the like. The concentration of the polymerization initiator is determined appropriately depending on the type of monomer, the molecular weight of the target polymer, and the reaction rate.

[0238] As the polymerization initiator, persulfates (e.g., ammonium persulfate), or organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide can be used alone or in the form of a mixture thereof. They may also be used in combination with a reducing agent such as sodium sulfite to form a redox system. Furthermore, during polymerization, a radical scavenger such as hydroquinone or catechol, or a peroxide decomposer such as ammonium sulfite, can be added to adjust the radical concentration in the system.

[0239] As the polymerization initiator, persulfates are particularly preferred because they can easily produce polymers with higher molecular weights. Examples of persulfates include ammonium persulfate, potassium persulfate, and sodium persulfate, with ammonium persulfate being preferred.

[0240] The amount of polymerization initiator to be added is not particularly limited, but may be added all at once, stepwise, or continuously at the beginning of polymerization in an amount (for example, several ppm relative to water concentration) that does not significantly decrease the polymerization rate. The upper limit is a range in which the reaction temperature can be increased while removing heat from the equipment using the heat of polymerization reaction, and a more preferred upper limit is a range in which the heat of polymerization reaction can be removed from the equipment.

[0241] In the production methods (11) to (13), the polymerization initiator can be added not only at the start of polymerization but also during polymerization. The ratio of the amount of polymerization initiator added at the start of polymerization to the amount of polymerization initiator added during polymerization is preferably 95 / 5 to 5 / 95, more preferably 60 / 40 to 10 / 90, and even more preferably 30 / 70 to 15 / 85. The method of adding the polymerization initiator during polymerization is not particularly limited, and the entire amount may be added at once, or may be added in two or more divided portions, or may be added continuously.

[0242] In the production methods (11) to (13), since a polymer having a higher molecular weight can be easily produced, the total amount of polymerization initiators used in the polymerization is preferably 0.00001 to 10% by mass relative to the aqueous medium. The total amount of polymerization initiators used in the polymerization is more preferably 0.0001% by mass or more, even more preferably 0.001% by mass or more, particularly preferably 0.01% by mass or more, more preferably 5% by mass or less, and even more preferably 2% by mass or less.

[0243] In the production methods (11) to (13), since a polymer having a higher molecular weight can be easily produced, the total amount of polymerization initiator used in the polymerization is preferably 0.001 to 10 mol% based on the monomers. The total amount of polymerization initiator used in the polymerization is more preferably 0.005 mol% or more, even more preferably 0.01 mol% or more, particularly preferably 0.1 mol% or more, most preferably 0.5 mol% or more, more preferably 5 mol% or less, even more preferably 2.5 mol% or less, particularly preferably 2.2 mol% or less, and most preferably 2.0 mol% or less.

[0244] In the production methods (11) to (13), since polymers with higher molecular weights can be easily produced, the amount of monomers containing monomers (11) to (13) present at the start of polymerization is preferably 30% by mass or more relative to the amount of aqueous medium present. The amount of monomer present is more preferably 30% by mass or more, and even more preferably 40% by mass or more. The upper limit of the amount of monomer present is not particularly limited, but may be 200% by mass or less from the viewpoint of smoothly progressing the polymerization. The amount of monomer present at the start of polymerization refers to the total amount of monomers (11) to (13) and, if present, other monomers present in the reactor at the start of polymerization.

[0245] In the production methods (11) to (13), the polymerization may be carried out in the presence of a pH adjuster, which may be added before or after the initiation of polymerization.

[0246] Examples of pH adjusters that can be used include ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium phosphate, potassium phosphate, sodium citrate, potassium citrate, ammonium citrate, sodium gluconate, potassium gluconate, and ammonium gluconate.

[0247] In the production methods (11) to (13), the polymerization of the monomers (11) to (13) can be carried out by charging a reactor with an aqueous medium, any of the monomers (11) to (13), and, if necessary, other monomers and, if necessary, other additives, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of polymerization initiator to initiate the polymerization reaction. After the initiation of the polymerization reaction, the monomer, polymerization initiator, and other additives may be added depending on the purpose.

[0248] In the production methods (11) to (13), the polymerization of the monomers can be carried out substantially in the absence of a fluorinated surfactant. In the present disclosure, "substantially in the absence of a fluorinated surfactant" means that the amount of the fluorinated surfactant relative to the aqueous medium is 10 ppm by mass or less. The amount of the fluorinated surfactant relative to the aqueous medium is preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably 10 ppb by mass or less, and even more preferably 1 ppb by mass or less.

[0249] As for the fluorine-containing surfactant, the details explained in the explanation of the polymerization of the fluoromonomer are also applicable to the production methods (11) to (13).

[0250] The content of the dimer and trimer of the monomer (I) represented by the general formula (I) in the composition is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, particularly preferably 0.001% by mass or less, and most preferably 0.0001% by mass or less, based on the polymer (I).

[0251] (Fluororubber) The composition of the present disclosure contains a fluororubber.

[0252] The fluororubber preferably has an ion exchange ratio (IXR) of greater than 53. Preferred fluororubbers have no ionic groups or a limited number of ionic groups that result in an ion exchange ratio greater than about 100. The ion exchange ratio of preferred fluororubbers is preferably 1,000 or greater, more preferably 2,000 or greater, and even more preferably 5,000 or greater.

[0253] The fluororubber in the composition of the present disclosure can be produced, for example, by the following method. That is, polymerization of the fluororubber is carried out by charging pure water and polymer (I) into a pressure-resistant reaction vessel equipped with a stirrer, deoxidizing, then charging monomers, bringing the temperature to a predetermined value, and adding a polymerization initiator to initiate the reaction. As the pressure decreases as the reaction progresses, additional monomers are continuously or intermittently supplied to maintain the initial pressure. Once a predetermined amount of monomer has been supplied, the supply is stopped, the monomers in the reaction vessel are purged, and the temperature is returned to room temperature to terminate the reaction. In this case, the polymer latex can be continuously removed from the reaction vessel.

[0254] In particular, when producing the above-mentioned fluororubber, as disclosed in International Publication No. 00 / 01741, it is possible to use a method in which fluoropolymer fine particles are first synthesized at a high concentration as described above, then diluted and further polymerized, thereby making it possible to increase the final polymerization rate compared to normal polymerization.

[0255] The polymerization conditions for the fluororubber are appropriately selected from the viewpoints of the desired properties of the polymer and control of the polymerization rate, and the polymerization temperature is usually −20 to 200° C., preferably 5 to 150° C., and the polymerization pressure is usually 0.5 to 10 MPaG, preferably 1 to 7 MPaG. The pH of the polymerization medium is preferably maintained at 1.5 to 13 by a known method or the like using a pH adjuster described below.

[0256] Fluoromonomers used in the polymerization of the fluororubber include, in addition to vinylidene fluoride, fluorine-containing ethylenically unsaturated monomers that have at least the same number of fluorine atoms as the carbon atoms and are copolymerizable with vinylidene fluoride. Examples of the fluorine-containing ethylenically unsaturated monomers include trifluoropropene, tetrafluoropropene, pentafluoropropene, hexafluoropropene, 2,3,3,3-tetrafluoropropene, hexafluorobutene, and octafluorobutene. Among these, hexafluoropropene and 2,3,3,3-tetrafluoropropene are particularly suitable due to the properties of the elastomer obtained when they block the crystal growth of the polymer. Examples of the fluorine-containing ethylenically unsaturated monomers include trifluoroethylene, TFE, and CTFE. Fluorine-containing monomers having one or more chlorine and / or bromine substituents can also be used. Perfluoro(alkyl vinyl ethers), such as perfluoro(methyl vinyl ether), can also be used. TFE and HFP are preferred for producing fluororubbers.

[0257] The fluoromonomer used for the polymerization of the above-mentioned fluororubber is preferably the one having at least one double bond.As the above-mentioned fluoromonomer, tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkyl ethylene, fluoroalkyl allyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, general formula (100): CHX １０１ =CX １０２ Rf １０１ (In the formula, X １０１ and X １０２ is H on one side and F on the other side, and Rf １０１ is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluorinated vinyl heterocycle, and a monomer that provides a crosslinking site.

[0258] Examples of the fluoroalkyl vinyl ether include those represented by the general formula (110): CF ２ =CF-ORf １１１ (wherein, Rf １１１ represents a perfluoroorganic group.) A fluoromonomer represented by general formula (120): CF ２ =CF-OCH ２ -Rf １２１ (wherein, Rf １２１ is a perfluoroalkyl group having 1 to 5 carbon atoms), a fluoromonomer represented by the general formula (130): CF ２ = CFOCF ２ ORf １３１ (wherein, Rf １３１ is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms and containing 1 to 3 oxygen atoms.) Fluoromonomers represented by general formula (140): CF ２ = CFO (CF ２ CF (Y １４１ ) O) ｍ (CF ２ ) ｎ F (wherein, Y １４１ represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4.) and a fluoromonomer represented by the general formula (150): CF ２ =CF-O-(CF ２ CFY １５１ -O) ｎ -(CFY １５２ ) ｍ -A １５１ (In the formula, Y １５１ represents a fluorine atom, a chlorine atom, -SO ２ It represents a F group or a perfluoroalkyl group. The perfluoroalkyl group is an etheric oxygen and -SO ２ The group n may contain an F group. n represents an integer of 0 to 3. １５１ may be the same or different. １５２ represents a fluorine atom, a chlorine atom, or —SO ２represents an F group, and m represents an integer of 1 to 5. １５２ may be the same or different. １５１ is -SO ２ X １５１ , -COZ １５１ or -POZ １５２ Z １５３ represents. １５１ is F, Cl, Br, I, -OR １５１ or -NR １５２ R １５３ Represents Z. １５１ , Z １５２ and Z １５３ are the same or different and represent -NR １５４ R １５５ Or -OR １５６ Represents R １５１ , R １５２ , R １５３ , R １５４ , R １５５ and R １５６ are the same or different and represent H, ammonium, an alkali metal, an alkyl group which may contain a fluorine atom, an aryl group, or a sulfonyl-containing group.

[0259] In the present disclosure, the term "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoroorganic group may have an ether oxygen atom.

[0260] The fluoromonomer represented by the general formula (110) is Rf １１１ is a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0261] Examples of the perfluoroorganic group in the general formula (110) include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. The fluoromonomer represented by the general formula (110) further includes a fluoromonomer represented by the general formula (110) in which Rf １１１is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, Rf １１１ is of the following formula:

[0262]

[0263] (wherein m represents 0 or an integer of 1 to 4), and Rf is a group represented by the following formula:

[0264] CF ３ CF ２ CF ２ -(O-CF(CF ３ )-CF ２ ) ｎ - (wherein n represents an integer of 1 to 4).

[0265] Among the fluoromonomers represented by the general formula (110), those represented by the general formula (160): CF ２ =CF-ORf １６１ (wherein, Rf １６１ Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms. １６１ is preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

[0266] The fluoroalkyl vinyl ether is preferably at least one selected from the group consisting of fluoromonomers represented by the general formulas (160), (130) and (140).

[0267] The fluoromonomer represented by general formula (160) is preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether), and more preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether) and perfluoro(propyl vinyl ether).

[0268] The fluoromonomer represented by the general formula (130) is CF ２ = CFOCF ２ OCF ３ , C.F. ２ = CFOCF ２OCF ２ CF ３ , and CF ２ = CFOCF ２ OCF ２ CF ２ OCF ３ It is preferable that the polymer is at least one selected from the group consisting of:

[0269] The fluoromonomer represented by the general formula (140) is CF ２ = CFOCF ２ CF (CF ３ ) O(CF ２ ) ３ F, CF ２ = CFO (CF ２ CF (CF ３ ) O) ２ (CF ２ ) ３ F and CF ２ = CFO (CF ２ CF (CF ３ ) O) ２ (CF ２ ) ２ It is preferable that the compound is at least one selected from the group consisting of F.

[0270] The fluoromonomer represented by the general formula (150) is CF ２ = CFOCF ２ CF ２ SO ２ F, CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ SO ２ F, CF ２ = CFOCF ２ CF (CF ２ CF ２ SO ２ F) OCF ２ CF ２ SO ２ F and CF ２ = CFOCF ２ CF (SO ２ F) ２ At least one selected from the group consisting of:

[0271] The fluoromonomer represented by the general formula (100) is Rf １０１ is a linear fluoroalkyl group, and Rf １０１ More preferred is a fluoromonomer in which Rf is a linear perfluoroalkyl group. １０１ The number of carbon atoms of the fluoromonomer represented by the general formula (100) is preferably 1 to 6. ２ =CFCF ３ , C.H. ２ =CFCF ２ CF ３ , C.H. ２ =CFCF ２ CF ２ CF ３ , C.H. ２ =CFCF ２ CF ２ CF ２ H, CH ２ =CFCF ２ CF ２ CF ２ CF ３ , CHF=CHCF ３ (E form), CHF=CHCF ３ (Z-isomer), among which CH ２ =CFCF ３ Preferred is 2,3,3,3-tetrafluoropropylene represented by the following formula:

[0272] The fluoroalkylethylene includes fluoroalkyl ethylenes represented by the general formula (170): CH ２ =CH-(CF ２ ) ｎ -X １７１ (In the formula, X １７１ is H or F, and n is an integer of 3 to 10.) is preferred, and CH ２ =CH-C ４ F ９ , and C.H. ２ =CH-C ６ F １３ It is more preferable that the polymer is at least one selected from the group consisting of:

[0273] Examples of the fluoroalkyl allyl ether include those represented by the general formula (180): CF ２=CF-CF ２ -ORf １１１ (wherein, Rf １１１ represents a perfluoroorganic group.

[0274] Rf of general formula (180) １１１ is Rf in general formula (110). １１１ Rf is the same as １１１ As the fluoroalkyl aryl ether represented by the general formula (180), a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms is preferred. ２ =CF-CF ２ -O-CF ３ , C.F. ２ =CF-CF ２ -O-C ２ F ５ , C.F. ２ =CF-CF ２ -O-C ３ F ７ , and CF ２ =CF-CF ２ -O-C ４ F ９ At least one selected from the group consisting of CF ２ =CF-CF ２ -O-C ２ F ５ , C.F. ２ =CF-CF ２ -O-C ３ F ７ , and CF ２ =CF-CF ２ -O-C ４ F ９ More preferably, at least one selected from the group consisting of CF ２ =CF-CF ２ -O-CF ２ CF ２ CF ３ is more preferable.

[0275] The fluorinated vinyl heterocycle may be a heterocyclic compound represented by the general formula (230): (In the formula, X ２３１ and X ２３２are independently F, Cl, a methoxy group, or a fluorinated methoxy group; Y ２３１ is the formula Y ２３２ or formula Y ２３３ is.

[0276] (In the formula, Z ２３１ and Z ２３２ are independently F or a fluorinated alkyl group having 1 to 3 carbon atoms.

[0277] The monomer that provides the crosslinking site is represented by the general formula (180): CX １８１ ２ =CX １８２ -R ｆ １８１ CHR １８１ X １８３ (In the formula, X １８１ and X １８２ are independently a hydrogen atom, a fluorine atom, or CH ３ , R ｆ １８１ represents a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R １８１ is a hydrogen atom or CH ３ , X １８３ is an iodine atom or a bromine atom, a fluoromonomer represented by general formula (190): CX １９１ ２ =CX １９２ -R ｆ １９１ X １９３ (In the formula, X １９１ and X １９２ are independently a hydrogen atom, a fluorine atom, or CH ３ , R ｆ １９１ represents a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, X １９３ is an iodine atom or a bromine atom.) A fluoromonomer represented by the general formula (200): CF ２ = CFO (CF ２ CF (CF ３ ) O) ｍ(CF ２ ) ｎ -X ２０１ (wherein m is an integer of 0 to 5, n is an integer of 1 to 3, X ２０１ represents a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ２ I.) and a fluoromonomer represented by the general formula (210): CH ２ =CFCF ２ O(CF(CF ３ )CF ２ O) ｍ (CF (CF ３ )) ｎ -X ２１１ (wherein m is an integer of 0 to 5, n is an integer of 1 to 3, X ２１１ represents a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ２ OH.) and a fluoromonomer represented by the general formula (220): CR ２２１ R ２２２ =CR ２２３ -Z ２２１ -CR ２２４ =CR ２２５ R ２２６ (In the formula, R ２２１ , R ２２２ , R ２２３ , R ２２４ , R ２２５ and R ２２６ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２２１ -(Q) is a linear or branched alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or an at least partially fluorinated alkylene or oxyalkylene group having 1 to 10 carbon atoms, which may contain an oxygen atom; ｐ -CF ２ O-(CF ２ CF ２ O) ｍ (CF ２ O) ｎ -CF ２ -(Q) ｐ- (wherein Q is an alkylene group or an oxyalkylene group, p is 0 or 1, and m / n is 0.2 to 5), and is a (per)fluoropolyoxyalkylene group having a molecular weight of 500 to 10,000.

[0278] X １８３ and X １９３ is preferably an iodine atom. ｆ １８１ and R ｆ １９１ is preferably a perfluoroalkylene group having 1 to 5 carbon atoms. １８１ is preferably a hydrogen atom. ２０１ represents a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ２ Preferably, X is I. ２１１ represents a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ２ It is preferably OH.

[0279] The monomer that provides the crosslinking site is CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ C.N., C.F. ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ COOH, CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CH ２ I, CF ２ = CFOCF ２ CF ２ CH ２ I, CH ２ =CFCF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) CN, CH ２ =CFCF ２ OCF (CF３ )CF ２ OCF (CF ３ ) COOH, CH ２ =CFCF ２ OCF (CF ３ )CF ２ OCF (CF ３ ) CH ２ OH, CH ２ = CHCF ２ CF ２ I, CH ２ =CH(CF ２ ) ２ CH=CH ２ , C.H. ２ =CH(CF ２ ) ６ CH=CH ２ , and CF ２ = CFO (CF ２ ) ５ CN, and CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CN and CF ２ = CFOCF ２ CF ２ CH ２ It is more preferable that the compound is at least one selected from the group consisting of I.

[0280] In the polymerization of the fluororubber, the polymer (I) is usually added in an amount of 0.0001 to 20% by mass, preferably 10% by mass or less, more preferably 2% by mass or less, based on 100% by mass of the aqueous medium.

[0281] In the polymerization of the fluororubber, known inorganic radical polymerization initiators can be used as the polymerization initiator. As the inorganic radical polymerization initiator, conventionally known water-soluble inorganic peroxides, such as sodium, potassium, and ammonium persulfates, perphosphates, perborates, percarbonates, or permanganates, are particularly useful. The radical polymerization initiator can be further activated with a reducing agent, such as sodium, potassium, or ammonium sulfites, bisulfites, metabisulfites, hyposulfites, thiosulfates, phosphites, or hypophosphites, or with easily oxidizable metal compounds, such as ferrous salts, cuprous salts, or silver salts. A preferred inorganic radical polymerization initiator is ammonium persulfate, and it is more preferred to use ammonium persulfate and sodium bisulfite in a redox system.

[0282] The concentration of the polymerization initiator added is appropriately determined depending on the molecular weight of the target fluoropolymer and the polymerization reaction rate, but is set to an amount of 0.0001 to 10% by mass, preferably 0.01 to 5% by mass, relative to 100% by mass of the total amount of monomers.

[0283] In the polymerization of the fluororubber, known chain transfer agents can be used, including hydrocarbons, esters, ethers, alcohols, ketones, chlorine compounds, carbonates, iodine compounds, etc. Among these, isopentane, diethyl malonate, and ethyl acetate are preferred from the viewpoint of being less likely to decrease the reaction rate, and I(CF ２ ) ４ I, I (CF ２ ) ６ I, ICH ２ Diiodine compounds such as I are preferred in that they can iodine the polymer terminals and can be used as reactive polymers.

[0284] The amount of the chain transfer agent used is usually 0.5×10 －３ ~5 x 10 －３ mol%, preferably 1.0×10 －３ ~3.5 x 10 －３ It is preferably expressed as mole percent.

[0285] In the polymerization of the fluororubber, phosphates, sodium hydroxide, potassium hydroxide, etc. can be preferably used as a pH adjuster.

[0286] The polymer dispersion obtained by the method for producing the composition has, at the time of completion of the polymerization, a solids concentration of 1.0 to 40% by mass, an average particle size of 0.03 to 1 μm, preferably 0.05 to 0.5 μm, and a number average molecular weight of 1,000 to 2,000,000.

[0287] Among the fluororubbers, perfluororubber (perfluoroelastomer) can be obtained by polymerizing a perfluoromonomer in an aqueous medium in the presence of polymer (I).

[0288] Perfluoromonomers include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and compounds represented by the general formula: CF ２ =CF-ORf １３ (wherein, Rf １３ represents a perfluoroalkyl group having 1 to 8 carbon atoms, a fluoromonomer represented by the general formula: CF ２ = CFOCF ２ ORf １４ (wherein, Rf １４ is 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 and containing 1 to 3 oxygen atoms), and ２ = CFO (CF ２ CF (Y １５ ) O) ｍ (CF ２ ) ｎ F (wherein, Y １５ represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4.

[0289] In the polymerization of perfluoromonomers, a monomer that provides a crosslinking site may be polymerized together with the perfluoromonomers.

[0290] The polymer (I) used in the method for producing a perfluoroelastomer preferably has an ion exchange capacity of 1.50 meq / g or more. The ion exchange capacities of the polymer (I) are, in order of increasing preference, 1.75 meq / g or more, 2.00 meq / g or more, 2.40 meq / g or more, 2.50 meq / g or more, 2.60 meq / g or more, 3.00 meq / g or more, and 3.50 meq / g or more. The ion exchange capacity is the content of ionic groups (anionic groups) in the polymer (I) and can be calculated from the composition of the polymer (I). The ion exchange capacity is determined by the content of precursor groups (for example, -COOCH ３ ) are not considered ionic groups for the purpose of determining the ion exchange capacity. It is presumed that the higher the ion exchange capacity of polymer (I), the more anionic groups there are in polymer (I), which leads to the formation of highly stable particles, and also leads to a higher number of particles per unit amount of water due to the high particle forming power, resulting in a higher polymerization rate.

[0291] The amount of polymer (I) added is preferably 0.01 to 20% by mass relative to 100% by mass of the aqueous medium. By setting the amount of polymer (I) added (abundance) in the polymerization within the above range, the polymerization reaction of the perfluoromonomer proceeds smoothly, and the perfluoroelastomer can be produced efficiently.

[0292] The amount of polymer (I) added is more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 0.75% by mass or more, and most preferably 1.0% by mass or more, relative to 100% by mass of the aqueous medium, because this allows the polymerization reaction of the perfluoromonomer to proceed more smoothly.

[0293] Furthermore, if the amount of polymer (I) added is too large, an effect commensurate with the amount added will not be obtained, which is economically disadvantageous, and there is also the possibility that post-treatment after polymerization will become complicated. Therefore, the amount of polymer (I) added is more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to 100% by mass of the aqueous medium.

[0294] The polymerization of the perfluoromonomer may be carried out in the presence of a polymerization initiator. The polymerization initiator is as described above. The amount of polymerization initiator added is preferably 0.0001 to 10% by mass, and more preferably 0.01 to 5% by mass, relative to 100% by mass of the perfluoromonomer. By setting the amount of polymerization initiator added (amount present) in the polymerization to be within the above range, the polymerization reaction of the perfluoromonomer proceeds smoothly, and the perfluoroelastomer can be produced efficiently. If the amount of polymerization initiator added is too small, a sufficient polymerization rate or a sufficient yield may not be obtained.

[0295] The polymerization of perfluoromonomer may be carried out in the presence of a pH adjuster. By carrying out the polymerization in the presence of a pH adjuster, it is possible to generate a sufficient number of perfluoroelastomer particles at a sufficient polymerization rate while further suppressing the adhesion of the perfluoroelastomer to the polymerization vessel. The pH adjuster may be added before or after the start of polymerization.

[0296] Examples of pH adjusters that can be used include ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, ammonium citrate, sodium gluconate, potassium gluconate, and ammonium gluconate.

[0297] Among the fluororubbers, the partially fluorinated rubber can be obtained by polymerizing a fluoromonomer in an aqueous medium in the presence of the polymer (I).

[0298] Fluoromonomers for obtaining partially fluorinated rubber include vinylidene fluoride (VdF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, iodine-containing fluorinated vinyl ethers, and fluorinated vinyl ethers represented by the general formula: CHX １ =CX ２ Rf (wherein, X １ and X ２ and Rf are each a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms.

[0299] In the method for producing the partially fluorinated rubber, it is preferable to polymerize at least vinylidene fluoride or tetrafluoroethylene as the fluoromonomer, and it is more preferable to polymerize vinylidene fluoride.

[0300] The amount of polymer (I) added is preferably 0.01 to 20% by mass relative to 100% by mass of the aqueous medium. By setting the amount of polymer (I) added (abundance) in the polymerization within the above range, the polymerization reaction of the fluoromonomer proceeds smoothly, and the partially fluorinated rubber can be produced efficiently. If the amount of polymer (I) added is too small, a sufficient polymerization rate or a sufficient yield may not be obtained.

[0301] The amount of polymer (I) added is more preferably 0.0001% by mass or more, still more preferably 0.0005% by mass or more, still more preferably 0.001% by mass or more, particularly preferably 0.005% by mass or more, and most preferably 0.01% by mass or more, relative to 100% by mass of the aqueous medium, because this allows the polymerization reaction of the fluoromonomer to proceed more smoothly.

[0302] Furthermore, if the amount of polymer (I) added is too large, an effect commensurate with the amount added will not be obtained, which is economically disadvantageous. Therefore, the amount of polymer (I) added is more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, relative to 100% by mass of the aqueous medium.

[0303] The polymerization of the fluoromonomer may be carried out in the presence of a polymerization initiator. The polymerization initiator is as described above. The amount of the polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the target partially fluorinated rubber, and the reaction rate. The amount of the polymerization initiator is appropriately determined depending on the molecular weight of the target partially fluorinated rubber and the polymerization reaction rate, and is preferably 0.00001 to 10% by mass, and more preferably 0.0001 to 1% by mass, relative to 100% by mass of the total amount of monomers.

[0304] The fluororubber may be a partially fluorinated rubber or a perfluororubber.

[0305] Partially fluorinated rubber has a methylene group (-CH ２ It is preferable that the main chain contains -CH ２ The partially fluorinated rubber containing - includes -CH ２ There is no particular limitation as long as it contains a chemical structure represented by -, and examples thereof include -CH ２ -CF ２ -, -CH ２ -CH(CH ３ ) -, -CH ２ -CH ２ -, -CH ２ -CF (CF ３ These can be introduced into the main chain of the partially fluorinated rubber by polymerizing, for example, vinylidene fluoride, propylene, ethylene, 2,3,3,3-tetrafluoropropylene, etc. The content of tetrafluoroethylene units in the partially fluorinated rubber (the content of polymerized units based on tetrafluoroethylene relative to the total polymerized units of the partially fluorinated rubber) may be less than 40 mol%.

[0306] Partially fluorinated rubbers include, for example, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and rubbers of the general formula: CF ２ =CF-Rf ａ (wherein, Rf ａ Ha-CF ３ or -ORf ｂ (Rf ｂ It is preferable that the partially fluorinated rubber contains a monomer unit based on at least one monomer selected from the group consisting of perfluoroethylenically unsaturated compounds represented by the formula (I) (where I is a perfluoroalkyl group having 1 to 5 carbon atoms) (for example, hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), etc.). Of these, it is preferable that the partially fluorinated rubber contains a VdF unit or a TFE unit.

[0307] Examples of partially fluorinated rubbers include vinylidene fluoride (VdF)-based fluororubbers, tetrafluoroethylene (TFE) / propylene (Pr)-based fluororubbers, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF)-based fluororubbers, ethylene / hexafluoropropylene (HFP)-based fluororubbers, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF)-based fluororubbers, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE)-based fluororubbers, Et / TFE / PAVE-based fluororubbers, etc. Among these, at least one selected from the group consisting of vinylidene fluoride-based fluororubbers and tetrafluoroethylene / propylene-based fluororubbers is preferred.

[0308] The vinylidene fluoride-based fluororubber is preferably a copolymer consisting of 45 to 85 mol % of vinylidene fluoride and 55 to 15 mol % of at least one other monomer copolymerizable with vinylidene fluoride, and more preferably a copolymer consisting of 50 to 80 mol % of vinylidene fluoride and 50 to 20 mol % of at least one other monomer copolymerizable with vinylidene fluoride.

[0309] Examples of at least one other monomer copolymerizable with the vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, and a compound represented by the general formula (100): CHX １０１ =CX １０２ Rf １０１ (In the formula, X １０１ and X １０２ is H on one side and F on the other side, and Rf １０１ is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluoromonomer represented by the general formula (170): CH ２ =CH-(CF ２ ) ｎ -X １７１ (In the formula, X １７１ is H or F, and n is an integer of 3 to 10. Examples of the fluoromonomer include a fluoromonomer represented by the general formula (160), a monomer that provides a crosslinking site, and a non-fluorinated monomer such as ethylene, propylene, or an alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, 2.3.3.3-tetrafluoropropene, a fluoroalkyl vinyl ether, and CTFE. As the fluoroalkyl vinyl ether, a fluoromonomer represented by the general formula (160) is preferred.

[0310] Specific examples of vinylidene fluoride-based fluororubbers include VdF / HFP-based rubbers, VdF / HFP / TFE-based rubbers, VdF / CTFE-based rubbers, VdF / CTFE / TFE-based rubbers, VdF / fluoromonomer-based rubbers represented by general formula (100), VdF / fluoromonomer-based rubbers represented by general formula (100) / TFE-based rubbers, VdF / perfluoro(methyl vinyl ether) [PMVE]-based rubbers, VdF / PMVE / TFE-based rubbers, VdF / PMVE / TFE / HFP-based rubbers, etc. Examples of VdF / fluoromonomer-based rubbers represented by general formula (100) include VdF / CH２ =CFCF ３ The VdF / fluoromonomer represented by the general formula (100) / TFE rubber is preferably VdF / TFE / CH ２ =CFCF ３ Rubbers based on ethylenediaminetetraacetic acid are preferred.

[0311] The vinylidene fluoride-based fluororubber is preferably a VdF / HFP copolymer or a VdF / HFP / TFE copolymer, and more preferably a VdF / HFP / TFE copolymer having a composition of (32-85) / (10-34) / (0-40) (mol%). The VdF / HFP / TFE composition is more preferably (32-85) / (15-34) / (0-34) (mol%), and even more preferably (47-81) / (17-32) / (0-28) (mol%).

[0312] For example, in the above VdF / HFP copolymer, the VdF / HFP composition is preferably (45 to 85) / (15 to 55) (mol%), more preferably (50 to 83) / (17 to 50) (mol%), still more preferably (55 to 81) / (19 to 45) (mol%), and particularly preferably (60 to 80) / (20 to 40) (mol%).

[0313] The above VdF / CH ２ =CFCF ３ The rubber is a rubber containing 40 to 99.5 mol% of VdF and CH ２ =CFCF ３ It is preferable that the copolymer is composed of 0.5 to 60 mol % of VdF, 50 to 85 mol % of CH ２ =CFCF ３ A copolymer consisting of 20 to 50 mol % is more preferred.

[0314] The VdF / TFE / PMVE rubber is preferably a copolymer having a VdF / TFE / PMVE composition of (32 to 85) / (3 to 40) / (10 to 34) mol %, and more preferably a copolymer having a VdF / TFE / PMVE composition of (45 to 81) / (4 to 30) / (16 to 28) mol %.

[0315] The Et / TFE / PAVE fluororubber preferably has an Et / TFE / PAVE composition of (10-40) / (32-60) / (20-40) (mol%), more preferably (20-40) / (40-50) / (20-30) (mol%). PMVE is preferred as the PAVE.

[0316] The tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer consisting of 45 to 70 mol % of tetrafluoroethylene, 55 to 30 mol % of propylene, and 0 to 5 mol % of a fluoromonomer that provides a crosslinking site.

[0317] The fluororubber may be a perfluororubber. The perfluororubber is preferably at least one selected from the group consisting of perfluororubbers containing TFE, such as TFE / fluoromonomer copolymers represented by general formula (160), (130) or (140) and TFE / fluoromonomer copolymers represented by general formula (160), (130) or (140) / monomer copolymers that provide crosslinking sites.

[0318] In the case of a TFE / PMVE copolymer, the composition is preferably 45-90 / 10-55 (mol %), more preferably 55-80 / 20-45, and even more preferably 55-70 / 30-45.

[0319] In the case of a copolymer of TFE / PMVE / monomer that provides a crosslinking site, the ratio is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), more preferably 55 to 77.9 / 20 to 49.9 / 0.1 to 3.5, and even more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.

[0320] In the case of TFE / fluoromonomer copolymer having 4 to 12 carbon atoms and represented by general formula (160), (130) or (140), it is preferably 50 to 90 / 10 to 50 (mol%), more preferably 60 to 88 / 12 to 40, and even more preferably 65 to 85 / 15 to 35.

[0321] In the case of TFE / fluoromonomer having 4 to 12 carbon atoms represented by general formula (160), (130) or (140) / monomer copolymer that provides crosslinking moieties, it is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol%), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3.

[0322] If the composition is outside these ranges, the rubber elastic properties will be lost and the properties will tend to become more like those of a resin.

[0323] The perfluororubber is preferably at least one selected from the group consisting of TFE / fluoromonomer copolymer represented by general formula (140) / crosslinkable moiety-providing fluoromonomer, TFE / perfluorovinyl ether copolymer represented by general formula (140), TFE / fluoromonomer copolymer represented by general formula (160), and TFE / fluoromonomer copolymer represented by general formula (160) / crosslinkable moiety-providing monomer copolymer.

[0324] Examples of the perfluororubber include those described in International Publication No. 97 / 24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, and Japanese Patent Publication No. 5-13961.

[0325] The fluororubber has a glass transition temperature of preferably −70° C. or higher, more preferably −60° C. or higher, and even more preferably −50° C. or higher, from the viewpoint of excellent compression set at high temperatures. Also, from the viewpoint of good cold resistance, the glass transition temperature is preferably 5° C. or lower, more preferably 0° C. or lower, and even more preferably −3° C. or lower.

[0326] The glass transition temperature can be determined by obtaining a DSC curve using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo) by heating 10 mg of a sample at a rate of 10°C / min, and determining the maximum value of the differential curve of the DSC curve at the time of second-order transition as the glass transition temperature.

[0327] In terms of good heat resistance, the fluororubber preferably has a Mooney viscosity ML(1+20) at 170°C of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In terms of good processability, the Mooney viscosity ML(1+20) is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

[0328] In terms of good heat resistance, the fluororubber preferably has a Mooney viscosity ML(1+20) at 140°C of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In terms of good processability, the Mooney viscosity ML(1+20) is preferably 180 or less, more preferably 150 or less, and even more preferably 110 or less.

[0329] In terms of good heat resistance, the fluororubber preferably has a Mooney viscosity ML(1+10) at 100°C of 10 or more, more preferably 20 or more, and even more preferably 30 or more. In terms of good processability, the Mooney viscosity ML(1+10) is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0330] The Mooney viscosity can be measured using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES at 170°C, 140°C, or 100°C in accordance with JIS K6300.

[0331] The above fluororubber can be processed into a fluororubber composition by adding a curing agent, a filler, etc.

[0332] Examples of the curing agent include polyols, polyamines, organic peroxides, organotin compounds, bis(aminophenol)tetraamines, and bis(thioaminophenols).

[0333] A fluororubber molded article can be obtained by molding the above-mentioned fluororubber. The molding method is not particularly limited, and includes known methods using the above-mentioned curing agents. Examples of molding methods include compression molding, casting, injection molding, extrusion molding, and rotocure molding, but are not limited to these.

[0334] When the fluororubber composition contains a curing agent (crosslinking agent), a crosslinked product can be obtained as a fluororubber molded article by crosslinking the fluororubber composition (crosslinkable composition). Examples of crosslinking methods that can be used include steam crosslinking, heat crosslinking, and radiation crosslinking, with steam crosslinking and heat crosslinking being preferred. Specific crosslinking conditions, which are not limited to these, are typically a temperature range of 140 to 250°C, a crosslinking time of 1 minute to 24 hours, and can be determined appropriately depending on the types of crosslinking accelerator, crosslinking agent, acid acceptor, etc.

[0335] The fluororubber molded article is suitable for use as a seal, a gasket, a wire coating, a hose, a tube, a laminate, an accessory, etc., and is particularly suitable for use as a part for semiconductor manufacturing equipment, an automobile part, etc.

[0336] The polymerization is preferably carried out by polymerizing a fluoromonomer substantially in the absence of a fluorine-containing surfactant (excluding compounds having a functional group reactive in radical polymerization and a hydrophilic group). Conventionally, a fluorine-containing surfactant has been used for the polymerization of a fluoromonomer in an aqueous medium, but according to the production method of the present disclosure, a fluororubber can be obtained even without using a fluorine-containing surfactant.

[0337] In the present disclosure, "substantially in the absence of a fluorinated surfactant" means that the amount of the fluorinated surfactant relative to the aqueous medium is 10 ppm by mass or less. The amount of the fluorinated surfactant relative to the aqueous medium is preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably 10 ppb by mass or less, and still more preferably 1 ppb by mass or less.

[0338] Examples of the fluorine-containing surfactant include anionic fluorine-containing surfactants, etc. The anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less excluding the anionic group.

[0339] The fluorine-containing surfactant may also be a surfactant containing fluorine, the molecular weight of the anionic moiety of which is 1,000 or less. The "anionic moiety" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF) represented by the formula (I) below may be used. ２ ) ｎ１ In the case of COOM, "F(CF ２ ) ｎ１ This is the "COO" part.

[0340] The fluorine-containing surfactant also includes a fluorine-containing surfactant having a Log POW of 3.5 or less. The Log POW is the partition coefficient between 1-octanol and water, and is expressed as Log P [where P represents the ratio of the fluorine-containing surfactant concentration in octanol to the fluorine-containing surfactant concentration in water when a 1:1 octanol / water mixture containing the fluorine-containing surfactant undergoes phase separation]. The Log POW can be measured using a column: TOSOH ODS-120T column (φ4.6 mm×250 mm, manufactured by Tosoh Corporation), an eluent: acetonitrile / 0.6% by mass HClO ４ HPLC is performed on standard substances (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) with known octanol / water partition coefficients under conditions of water=1 / 1 (vol / vol %), flow rate: 1.0 ml / min, sample amount: 300 μL, column temperature: 40°C, and detection light: UV 210 nm. A calibration curve is prepared between each elution time and the known octanol / water partition coefficient, and the elution time is calculated from the HPLC elution time of the sample solution based on this calibration curve.

[0341] Specific examples of the fluorine-containing surfactants include those described in U.S. Patent Application Publication Nos. 2007 / 0015864, 2007 / 0015865, 2007 / 0015866, 2007 / 0276103, 2007 / 0117914, 2007 / 142541, 2008 / 0015319, and U.S. Pat. No. 3,250,808. , U.S. Patent No. 3,271,341, JP 2003-119204 A, WO 2005 / 042593, WO 2008 / 060461, WO 2007 / 046377, JP 2007-119526 A, WO 2007 / 046482, WO 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, WO 2013 / 189824, and those described in WO 2013 / 189826, and the like.

[0342] The anionic fluorine-containing surfactant may be a compound represented by the following general formula (N ０ ): X ｎ０ -Rf ｎ０ -Y ０ (N ０ ) (wherein, X ｎ０ is H, Cl or F. ｎ０ is a linear, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which some or all of the H atoms are substituted with F, and the alkylene group may contain one or more ether bonds, and some of the H atoms may be substituted with Cl. ０ is an anionic group. ０ The anionic group is -COOM, -SO ２ M or -SO ３ M, -COOM or -SO ３ M. M may be H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７is H or an organic group. The metal atom includes alkali metals (Group 1), alkaline earth metals (Group 2), etc., such as Na, K, or Li. ７ As the group, H or C １－１０ and may be an organic group of the formula: １－４ and may be an organic group of the formula: １－４ M may be H, a metal atom, or an alkyl group of the formula NR ７ ４ may be H, an alkali metal (Group 1), an alkaline earth metal (Group 2), or NR ７ ４ may be H, Na, K, Li or NH ４ The above Rf ｎ０ may be one in which 50% or more of H is substituted with fluorine.

[0343] The general formula (N ０ The compound represented by the following general formula (N １ ): X ｎ０ -(CF ２ ) ｍ１ -Y ０ (N １ ) (wherein, X ｎ０ is H, Cl, and F, m1 is an integer from 3 to 15, and Y ０ is as defined above), a compound represented by the following general formula (N ２ ): Rf ｎ１ -O-(CF(CF ３ )CF ２ O) ｍ２ CFX ｎ１ -Y ０ (N ２ ) (wherein, Rf ｎ１ is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, and X ｎ１ is F or CF ３ and Y ０ is as defined above), a compound represented by the following general formula (N ３ ): Rf ｎ２ (CH ２ ) ｍ３ -(Rf ｎ３ ) ｑ-Y ０ (N ３ ) (wherein, Rf ｎ２ is a partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, m3 is an integer of 1 to 3, and Rf ｎ３ is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y ０ is as defined above), a compound represented by the following general formula (N ４ ): Rf ｎ４ -O-(CY ｎ１ Y ｎ２ ) ｐ CF ２ -Y ０ (N ４ ) (wherein, Rf ｎ４ is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain ether bonds and / or chlorine atoms; Y ｎ１ and Y ｎ２ are the same or different and are H or F, p is 0 or 1, and Y ０ is as defined above.) and a compound represented by the general formula (N ５ ): (In the formula, X ｎ２ , X ｎ３ and X ｎ４ Rf may be the same or different and are H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether linkage. ｎ５ is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms, which may contain an ether bond; L is a linking group; Y ０ is as defined above, where X ｎ２ , X ｎ３ , X ｎ４ and Rf ｎ５ wherein the total number of carbon atoms is 18 or less.

[0344] The general formula (N ０) More specifically, the compounds represented by the formula (I) below include perfluorocarboxylic acids (I), ω-H perfluorocarboxylic acids (II), perfluoroether carboxylic acids (III), perfluoroalkyl alkylene carboxylic acids (IV), perfluoroalkoxy fluorocarboxylic acids (V), perfluoroalkyl sulfonic acids (VI), ω-H perfluoro sulfonic acids (VII), perfluoroalkyl alkylene sulfonic acids (VIII), alkyl alkylene carboxylic acids (IX), fluorocarboxylic acids (X), alkoxy fluorosulfonic acids (XI), alkoxy fluorosulfonic acids (XI), and the like.

[0345] The perfluorocarboxylic acid (I) is represented by the following general formula (I): F(CF ２ ) ｎ１ COOM (I) (wherein n1 is an integer of 3 to 14, and M is H, a metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0346] The ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II): H(CF ２ ) ｎ２ COOM (II) (wherein n2 is an integer of 4 to 15, and M is as defined above).

[0347] The perfluoroethercarboxylic acid (III) is a compound represented by the following general formula (III): １ -O-(CF(CF ３ )CF ２ O) ｎ３CF (CF ３ ) COOM (III) (wherein, Rf １ is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.

[0348] The perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV): ２ (CH ２ ) ｎ４ Rf ３ COOM (IV) (wherein, Rf ２ is a perfluoroalkyl group having 1 to 5 carbon atoms, and 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 as defined above.

[0349] The alkoxyfluorocarboxylic acid (V) is represented by the following general formula (V): Rf ４ -O-CY １ Y ２ CF ２ -COOM (V) (wherein, Rf ４ is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain ether bonds and / or chlorine atoms; Y １ and Y ２ are the same or different and are H or F, and M is as defined above.

[0350] The perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI): F(CF ２ ) ｎ５ SO ３ M (VI) (wherein n5 is an integer of 3 to 14, and M is as defined above).

[0351] The ω-H perfluorosulfonic acid (VII) is represented by the following general formula (VII): H(CF ２ ) ｎ６ SO ３M (VII) (wherein n6 is an integer of 4 to 14, and M is as defined above).

[0352] The perfluoroalkyl alkylene sulfonic acid (VIII) is a compound represented by the following general formula (VIII): ５ (CH ２ ) ｎ７ SO ３ M (VIII) (wherein, Rf ５ is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.

[0353] The alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX): ６ (CH ２ ) ｎ８ COOM (IX) (wherein, Rf ６ is a linear or branched partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer from 1 to 3, and M is as defined above.

[0354] The fluorocarboxylic acid (X) is represented by the following general formula (X): ７ -O-Rf ８ -O-CF ２ -COOM (X) (wherein, Rf ７ is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, which may contain an ether bond and / or a chlorine atom, and Rf ８ is a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is as defined above.

[0355] The alkoxyfluorosulfonic acid (XI) is represented by the following general formula (XI): Rf ９ -O-CY １ Y ２ CF ２ -SO ３ M (XI) (wherein, Rf ９is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, and which is partially or completely fluorinated; Y １ and Y ２ are the same or different and are H or F, and M is as defined above.

[0356] The compound (XII) is represented by the following general formula (XII): (In the formula, X １ , X ２ and X ３ Rf may be the same or different and are H, F and linear or branched partially or fully fluorinated alkyl groups having 1 to 6 carbon atoms, which may contain ether bonds; １０ is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y ０ is an anionic group. ０ is -COOM, -SO ２ M or -SO ３ M, and -SO ３ M or COOM (wherein M is as defined above). Examples of L include a single bond and a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms which may contain an ether bond.

[0357] The compound (XIII) has the following general formula (XIII): １１ -O-(CF ２ CF (CF ３ ) O) ｎ９ (CF ２ O) ｎ１０ CF ２ COOM (XIII) (wherein, Rf １１ is a fluoroalkyl group containing chlorine and having 1 to 5 carbon atoms, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above. ２ ClO(CF ２ CF (CF ３ ) O) ｎ９ (CF ２ O) ｎ１０CF ２ COONH ４ (a mixture having an average molecular weight of 750, wherein n9 and n10 are defined above).

[0358] As mentioned above, examples of the anionic fluorine-containing surfactant include carboxylic acid surfactants and sulfonic acid surfactants.

[0359] The fluorine-containing surfactant may be one type of fluorine-containing surfactant or a mixture containing two or more types of fluorine-containing surfactants.

[0360] Examples of the fluorine-containing surfactant include compounds represented by the following formula: The fluorine-containing surfactant may be a mixture of these compounds. In one embodiment of the above polymerization, the fluoromonomer is polymerized substantially in the absence of a compound represented by the following formula: F(CF ２ ) ７ COOM, F(CF ２ ) ５ COOM, H(CF ２ ) ６ COOM, H(CF ２ ) ７ COOM, C.F. ３ O (CF ２ ) ３ OCHFCF ２ COOM, C.F. ３ (CF ２ ) ５ CH ２ CH ２ SO ３ M, C ３ F ７ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM, C.F. ３ CF ２ CF ２ OCF (CF ３ ) COOM, C.F. ３ CF ２ OCF ２ CF ２ OCF ２ COOM, C. ２ F ５ OCF (CF ３)CF ２ OCF (CF ３ ) COOM, C.F. ３ OCF (CF ３ )CF ２ OCF (CF ３ ) COOM, C.F. ２ ClCF ２ CF ２ OCF (CF ３ )CF ２ OCF ２ COOM, C.F. ２ ClCF ２ CF ２ OCF ２ CF (CF ３ ) OCF ２ COOM, C.F. ２ ClCF(CF ３ ) OCF (CF ３ )CF ２ OCF ２ COOM, C.F. ２ ClCF(CF ３ ) OCF ２ CF (CF ３ ) OCF ２ COOM, (In each formula, M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７ is H or an organic group.

[0361] (Aqueous Medium) The aqueous medium used in the method for producing the composition refers to 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 fluorine-free organic solvent such as an alcohol, an ether, or a ketone, and / or a fluorine-containing organic solvent having a boiling point of 40° C. or lower.

[0362] By polymerizing the fluoromonomer in an aqueous medium, a polymerization dispersion containing a fluororubber, the polymer (I), and the aqueous medium can be prepared. The content (solids concentration) of the fluororubber in the polymerization dispersion is usually 10 to 50% by mass, more preferably 15% by mass or more, and preferably 40% by mass or less, and more preferably 35% by mass or less.

[0363] The content of the fluororubber in the polymer dispersion is a value obtained by drying 1 g of the polymer dispersion in a blower dryer under conditions of 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 (1 g) of the polymer dispersion as a percentage.

[0364] (Form of Composition and Other Ingredients) The form of the composition of the present disclosure is not particularly limited, and may be gum, crumb, powder, pellet, etc., and is preferably gum or crumb. Gum is a small granular mass made of fluororubber, and crumb is an amorphous mass formed when fluororubber cannot maintain its small granular shape as a gum at room temperature and fuses together. Gum or crumb is preferably obtained by drying the coagulation product obtained by coagulation.

[0365] In one embodiment of the composition of the present disclosure, the composition contains a fluorine-containing surfactant. The composition containing the fluorine-containing surfactant has the advantage that it can be produced stably with high productivity using the fluorine-containing surfactant.

[0366] In one embodiment of the composition of the present disclosure, the composition is substantially free of a fluorine-containing surfactant. A composition substantially free of a fluorine-containing surfactant needs to be produced by polymerizing a fluoromonomer without using a fluorine-containing surfactant, but this production becomes possible by the production method of the present disclosure using polymer (I).

[0367] In the present disclosure, the phrase "substantially free of fluorinated surfactant" means that the content of fluorinated surfactant in the composition is 10 ppm by mass or less, preferably 1 ppm by mass or less, more preferably 100 ppb by mass or less, even more preferably 10 ppb by mass or less, still more preferably 1 ppb by mass or less, and particularly preferably below the detection limit of the fluorinated surfactant as measured by liquid chromatography-mass spectrometry (LC / MS).

[0368] The content of the fluorine-containing surfactant can be quantified by known methods. For example, it can be quantified by LC / MS analysis. First, methanol is added to the composition to perform extraction, and the obtained extract is analyzed by LC / MS. To further improve the extraction efficiency, treatments such as Soxhlet extraction and ultrasonic treatment may be performed. Molecular weight information is extracted from the obtained LC / MS spectrum, and a match with the structural formula of the candidate fluorine-containing surfactant is confirmed. Thereafter, aqueous solutions containing five or more levels of the confirmed fluorine-containing surfactant are prepared, and LC / MS analysis is performed on the aqueous solutions containing each level. The relationship between the content and the area relative to the content is plotted, and a calibration curve is drawn. Then, using the calibration curve, the area of ​​the LC / MS chromatogram of the fluorine-containing surfactant in the extract can be converted to the content of the fluorine-containing surfactant.

[0369] (Method for Producing Composition) As described above, the composition of the present disclosure can be produced by polymerizing a fluoromonomer in an aqueous medium in the presence of polymer (I) to obtain a polymerization dispersion containing a fluororubber, and then subjecting the resulting polymerization dispersion to any of the following treatments. In this production method, the fluororubber can be coagulated without using a coagulant containing an inorganic acid or a metal element. (1) The fluororubber in the polymerization dispersion is brought into contact with an alcohol having 3 to 6 carbon atoms per OH group to coagulate the fluororubber. (2) The polymerization dispersion is frozen to coagulate the fluororubber. (3) The fluororubber in the polymerization dispersion is brought into contact with an extremely limited type of organic solvent to coagulate the fluororubber.

[0370] By polymerizing a fluoromonomer in an aqueous medium in the presence of polymer (I), a so-called emulsion polymerization reaction proceeds, and a polymerization dispersion in which fluororubber particles are dispersed in an aqueous medium is usually obtained.The fluororubber particles are then coagulated, so that the fluororubber in the polymerization dispersion can be recovered.Next, the coagulation methods (1) to (3) will be described in more detail.

[0371] (Coagulation Method (1)) (1) The fluororubber in the polymer dispersion is brought into contact with an alcohol having 3 to 6 carbon atoms per OH group to coagulate the fluororubber.

[0372] The alcohol may be any of a monohydric alcohol, a dihydric alcohol, and a trihydric alcohol. As the alcohol, a monohydric alcohol is preferable because it further improves the efficiency of removing the polymer (I). The alcohol may also be a non-fluorinated alcohol.

[0373] The number of carbon atoms per OH group of the alcohol is 3 to 6, preferably 4 or more and preferably 5 or less, since this further improves the efficiency of removing the polymer (I).

[0374] Examples of alcohols include: alcohols having 3 carbon atoms per OH group, such as 1-propanol and 2-propanol; alcohols having 4 carbon atoms per OH group, such as 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and 1,4-cyclohexanedimethanol; alcohols having 5 carbon atoms per OH group, such as 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, and 2-methyl-2-butanol; Alcohols having 6 carbon atoms per OH group such as 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, and 2-ethyl-1-butanol; and the like.

[0375] The alcohol may be partially substituted with halogen atoms. Examples of alcohols partially substituted with halogen atoms include 2,2,3,3,3-pentafluoro-1-propanol, 2-(perfluorobutyl)ethanol, 1H,1H,3H-tetrafluoropropanol, and 1H,1H,5H-octafluoropentanol.

[0376] The alcohol preferably has a MolLogP in the range of 0.3 to 1.6, more preferably 1.2 or less, since this further improves the efficiency of removing the polymer (I).

[0377] Examples of alcohols having a MolLogP value in the range of 0.3 to 1.6 include 2-methyl-1-propanol, 2-butanol, and 1-pentanol.

[0378] MolLogP is the octanol / water partition coefficient of a compound calculated using the open source library RDKit.

[0379] Of these, the alcohol is preferably at least one selected from the group consisting of 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol.

[0380] For coagulation, alcohol alone may be used, or a composition containing alcohol and an aqueous medium may be used.

[0381] The method for contacting the fluororubber in the polymerization dispersion with the alcohol is not particularly limited, and examples thereof include a method of adding the polymerization dispersion to the alcohol and a method of adding the alcohol to the polymerization dispersion.The mixture containing the polymerization dispersion and the alcohol may be stirred to sufficiently contact the fluororubber with the alcohol, thereby coagulating the fluororubber in the polymerization dispersion.Furthermore, the coagulation of the fluororubber may be carried out by a batch method or a continuous method.

[0382] As a method for contacting the fluororubber in the polymer dispersion with the alcohol, a method in which the polymer dispersion obtained by polymerization is dropped or added to the alcohol or a composition containing the alcohol is preferred, because this further improves the efficiency of removing the polymer (I).

[0383] Before coagulation, the content of the fluororubber in the polymer dispersion obtained by polymerization may be adjusted using water. The content of the fluororubber in the polymer dispersion used for coagulation may be 5 to 40% by mass relative to the polymer dispersion.

[0384] The amount of alcohol used for coagulation is preferably 0.5 times or more in weight relative to the weight (dry weight) of the fluororubber in the polymerization dispersion used for coagulation, because the removal efficiency of polymer (I) is further improved.The amount of alcohol used for coagulation is more preferably 1.0 times or more, more preferably 1.5 times or more.If the amount of alcohol is too small, coagulation becomes incomplete, and there is a risk of problems such as polymer loss and device blockage trouble.There is no particular upper limit to the amount of alcohol, but from the viewpoint of economic efficiency and device capacity, it is preferably 40 times or less, more preferably 10 times or less, and even more preferably 5 times or less.

[0385] Before contacting the fluororubber in the polymerization dispersion with the alcohol, the polymerization dispersion obtained by polymerization may be appropriately diluted with water. In one embodiment, the fluororubber and alcohol are contacted using a polymerization dispersion obtained by polymerization having a fluororubber concentration of 20 to 40% relative to water. In one embodiment, the polymerization dispersion obtained by polymerization is diluted with water, and the fluororubber and alcohol are contacted using the polymerization dispersion with an adjusted fluororubber concentration. The dilution ratio is preferably 1 to 10 times, more preferably 1 to 6 times, and even more preferably 1.5 to 4 times, based on the polymerization dispersion as 1. If the dilution ratio is too high, coagulation tends to be incomplete, and if the dilution ratio is too low, the number of washings tends to increase. Furthermore, before contacting the fluororubber in the polymerization dispersion with the alcohol, the alcohol may be diluted with water.

[0386] The temperature at which the fluororubber in the polymer dispersion is brought into contact with the alcohol is preferably 1 to 70°C, more preferably 5°C or higher, even more preferably 10°C or higher, more preferably 50°C or lower, even more preferably 40°C or lower, and particularly preferably 35°C or lower, because this further improves the efficiency of removing polymer (I).

[0387] Before coagulation, the pH of the polymer dispersion obtained by polymerization may be adjusted. The pH of the polymer dispersion when the fluororubber in the polymer dispersion is brought into contact with the alcohol is preferably within the range of 3 to 10, more preferably 4 or more, even more preferably 5 or more, more preferably 9 or less, and even more preferably 8 or less, for the purpose of suppressing corrosion of the equipment used in the coagulation process. Furthermore, when equipment made of a corrosion-resistant material such as a resin lining is used in the coagulation process, the pH of the polymer dispersion does not need to be adjusted.

[0388] The pH can be adjusted by adding an acid or alkali to the polymer dispersion. For example, if the pH of the polymer dispersion is too low, an alkali such as ammonia can be added to the polymer dispersion to adjust the pH of the polymer dispersion to within the above range.

[0389] When coagulation is carried out by contacting the fluororubber in the polymer dispersion with an alcohol, the polymer (I) is removed from the obtained coagulated product, but it is preferable to further wash the obtained coagulated product because this further improves the efficiency of removing the polymer (I).

[0390] By coagulating the fluororubber using the coagulation method (1) and washing the obtained coagulated product with water under appropriate conditions, a composition with a further reduced content of polymer (I) can be obtained. By washing the coagulated product with water under appropriate conditions, for example, the content of polymer (I) can be reduced to less than 0.1% by mass, preferably 0.05% by mass or less, and more preferably 0.02% by mass or less, based on the fluororubber.

[0391] The total amount of water used to wash the coagulate is preferably an amount equivalent to 1 to 100 times the mass of the coagulate, more preferably an amount equivalent to 10 times or more, even more preferably an amount equivalent to 20 times or more, more preferably an amount equivalent to 80 times or less, and even more preferably an amount equivalent to 60 times or less. When washing is performed two or more times, the total amount of water used to wash the coagulate is the total amount of water used in each washing.

[0392] The temperature of the water used to wash the coagulate is preferably 10 to 50°C.

[0393] The washing of the coagulated material can be carried out once or twice or more times. The washing method is not particularly limited, but can be carried out, for example, by a method in which the coagulated material and water are put into a washing tank and stirred. When washing is carried out twice or more, the coagulated material and water are put into a washing tank, stirred, and dehydrated repeatedly. The number of times the coagulated material is washed is preferably two or more times, more preferably three or more times, and preferably 10 or less times, more preferably 6 or less times.

[0394] After the fluororubber is coagulated or washed, the fluororubber can be dried.

[0395] (Coagulation Method (2)) (2) The polymer dispersion is frozen to coagulate the fluororubber.

[0396] After freezing the polymerization dispersion, the frozen polymerization dispersion is melted, so that the fluororubber can be coagulated.Furthermore, in order to reduce the content of the polymer (I) in the fluororubber, the alcohol that can be used in the coagulation method (1) or the organic solvent that can be used in the coagulation method (3) can be added as an auxiliary to the polymerization dispersion in a small amount to the extent that the polymerization dispersion does not coagulate, and then mixed, and then freeze-coagulation can be carried out.

[0397] The temperature at which the polymer dispersion is frozen is not particularly limited and may be equal to or lower than the temperature at which the polymer dispersion freezes. The freezing temperature is preferably 0 to −196° C., more preferably −5 to −50° C., and more preferably −10 to −30° C. If the freezing temperature is too high, coagulation may be insufficient, while if the freezing temperature is too low, excessive energy may be required, which may be economically disadvantageous.

[0398] The temperature at which the frozen polymer dispersion is melted is not particularly limited and may be equal to or higher than the temperature at which the polymer dispersion melts and lower than the thermal decomposition temperature of the fluororubber. The melting temperature is preferably 0 to 100°C, more preferably 5°C or higher, and more preferably 70°C or lower.

[0399] When coagulation is carried out by freezing the polymer dispersion, the polymer (I) is removed from the obtained coagulate, but it is preferable to further wash the obtained coagulate, since this further improves the efficiency of removing the polymer (I).

[0400] After the fluororubber is coagulated or washed, the fluororubber can be dried.

[0401] (Coagulation Method (3)) (3) The fluororubber in the polymer dispersion is brought into contact with an extremely limited type of organic solvent to coagulate the fluororubber.

[0402] As the organic solvent, at least one selected from the group consisting of the following compounds can be used: Carboxylic acid having 2 to 5 carbon atoms Methyl ethyl ketone Methyl acetate Dimethyl carbonate Acetone 3-methyl-2-cyclopentenone Methyl propionate Ethyl acetate Tetrahydrofuran 1,2-dimethoxyethane

[0403] Examples of the carboxylic acid having 2 to 5 carbon atoms include acetic acid, propionic acid, ethoxyacetic acid, and valeric acid.

[0404] For the coagulation, an organic solvent alone may be used, or a composition containing an organic solvent and an aqueous medium may be used.

[0405] The method for contacting the fluororubber with the organic solvent is not particularly limited, and examples thereof include a method of adding the polymer dispersion to the organic solvent and a method of adding the organic solvent to the polymer dispersion.The mixture containing the polymer dispersion and the organic solvent may be stirred to sufficiently contact the fluororubber with the organic solvent, thereby coagulating the fluororubber in the polymer dispersion.Furthermore, the coagulation of the fluororubber may be carried out by a batch method or a continuous method.

[0406] As a method for contacting the fluororubber with the organic solvent, a method in which the polymer dispersion obtained by polymerization is dropped or added to the organic solvent or a composition containing the organic solvent is preferred, because this further improves the efficiency of removing the polymer (I).

[0407] Before coagulation, the content of the fluororubber in the polymer dispersion obtained by polymerization may be adjusted using water. The content of the fluororubber in the polymer dispersion used for coagulation may be 5 to 40% by mass relative to the polymer dispersion.

[0408] The amount of organic solvent used for coagulation is preferably the weight equivalent to 0.5 times or more of the weight (dry weight) of the fluororubber in the polymerization dispersion used for coagulation, because the removal efficiency of polymer (I) is further improved.The amount of organic solvent used for coagulation is more preferably 1.0 times or more, more preferably 1.5 times or more.If the amount of organic solvent is too small, coagulation is incomplete, and there is a risk of problems such as polymer loss and device blockage trouble.There is no particular upper limit to the amount of organic solvent, but from the viewpoint of economic efficiency and device capacity etc., it is preferably 40 times or less, more preferably 10 times or less, more preferably 5 times or less.

[0409] Before contacting the fluororubber in the polymerization dispersion with the organic solvent, the polymerization dispersion obtained by polymerization may be appropriately diluted with water. In one embodiment, the fluororubber and the organic solvent are contacted using a polymerization dispersion obtained by polymerization with a fluororubber concentration of 20 to 40% relative to water. In one embodiment, the polymerization dispersion obtained by polymerization is diluted with water, and the fluororubber and the organic solvent are contacted using the polymerization dispersion with the adjusted fluororubber concentration. The dilution ratio is preferably 1 to 10 times, more preferably 1 to 6 times, and even more preferably 1.5 to 4 times, based on the polymerization dispersion as 1. If the dilution ratio is too high, coagulation tends to be incomplete, and if the dilution ratio is too low, the number of washings tends to increase. Furthermore, before contacting the fluororubber in the polymerization dispersion with the organic solvent, the organic solvent may be diluted with water.

[0410] The temperature at which the fluororubber in the polymer dispersion is brought into contact with the organic solvent is preferably 1 to 70°C, more preferably 5°C or higher, even more preferably 10°C or higher, more preferably 50°C or lower, even more preferably 40°C or lower, and particularly preferably 35°C or lower, because this further improves the efficiency of removing polymer (I).

[0411] Before coagulation, the pH of the polymer dispersion obtained by polymerization may be adjusted. For the purpose of suppressing corrosion of equipment used in the coagulation process, the pH of the polymer dispersion when the fluororubber in the polymer dispersion is brought into contact with the organic solvent is preferably within the range of 3 to 10, more preferably 4 or more, even more preferably 5 or more, more preferably 9 or less, and even more preferably 8 or less. Furthermore, when equipment made of a corrosion-resistant material such as a resin lining is used in the coagulation process, it is not necessary to adjust the pH of the polymer dispersion.

[0412] The pH can be adjusted by adding an acid or alkali to the polymer dispersion. For example, if the pH of the polymer dispersion is too low, an alkali such as ammonia can be added to the polymer dispersion to adjust the pH of the polymer dispersion to within the above range.

[0413] When coagulation is carried out by contacting the fluororubber in the polymer dispersion with an organic solvent, the polymer (I) is removed from the obtained coagulated product. However, it is preferable to further wash the obtained coagulated product, since this further improves the efficiency of removing the polymer (I).

[0414] After the fluororubber is coagulated or washed, the fluororubber can be dried.

[0415] Next, the crosslinkable composition (fluororubber composition) of the present disclosure will be described in detail. The crosslinkable composition of the present disclosure preferably contains a perfluoroelastomer as the fluororubber.

[0416] The crosslinkable composition of the present disclosure contains the above-described composition and at least one selected from the group consisting of an inorganic nitride, an organotin compound, an ammonia-generating compound, and a crosslinking agent. A crosslinked product can be obtained by crosslinking the crosslinkable composition of the present disclosure.

[0417] The inorganic nitride is not particularly limited, but silicon nitride (Si ３ N ４), lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, zirconium nitride, etc. Among these, silicon nitride is preferred because it can be supplied as nano-sized fine particles.

[0418] Examples of the organotin compounds include tetraphenyltin and triphenyltin.

[0419] The compound that generates ammonia is preferably a compound that generates ammonia at 40 to 330°C.

[0420] The ammonia-generating compound is preferably urea or its derivatives, or an ammonium salt, more preferably urea or an ammonium salt, and even more preferably urea. The ammonium salt may be an organic ammonium salt or an inorganic ammonium salt. The ammonia-generating compound may also be one that reacts with a trace amount of water to generate ammonia.

[0421] Examples of urea derivatives include biurea, thiourea, urea hydrochloride, and biuret.

[0422] Examples of organic ammonium salts include compounds described in JP-A-9-111081, WO-A-00 / 09603, and WO-A-98 / 23675, such as ammonium salts of polyfluorocarboxylic acids such as ammonium perfluorohexanoate and ammonium perfluorooctanoate; ammonium salts of polyfluorosulfonic acids such as ammonium perfluorohexane sulfonate and ammonium perfluorooctane sulfonate; ammonium salts of polyfluoroalkyl group-containing phosphoric or phosphonic acids such as ammonium perfluorohexane phosphate and ammonium perfluorooctane phosphate; and ammonium salts of non-fluorine-based carboxylic or sulfonic acids such as ammonium benzoate, ammonium adipate, and ammonium phthalate.

[0423] Examples of inorganic ammonium salts include compounds described in JP-A-9-111081, such as ammonium sulfate, ammonium carbonate, ammonium nitrate, and ammonium phosphate.

[0424] In addition, examples of the ammonia-generating compound include acetaldehyde ammonia, hexamethylenetetramine, formamidine, formamidine hydrochloride, formamidine acetate, t-butyl carbamate, benzyl carbamate, and HCF. ２ CF ２ CH (CH ３ ) OCONH ２ , phthalamide, and the like.

[0425] Examples of the crosslinking agent include crosslinking agents used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking.

[0426] The crosslinking agent used in peroxide crosslinking may be any organic peroxide that can easily generate peroxy radicals in the presence of heat or a redox system, and specific examples thereof include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide (Perbutyl D), t-butylcumyl peroxide (Perbutyl C), dicumyl peroxide (Percumyl D, Percumyl D-40, Percumyl D-40MB(T)), α,α- Bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, Perhexa 25B-40), 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3 (Perhexyne 25B, Perhexyne 25B-40), benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (Perhexa 25Z), t-butylperoxymaleic acid (t-butyl MA), t-butyl Chilperoxy isopropyl carbonate (Perbutyl I-75), methyl ethyl ketone peroxide (Permec D (DR), Permec H (HR, HY), Permec N (NR, NY), Permec S (SR), Permec F (FR), Permec G (GR, GY)), cyclohexanone peroxide (Perhexa H), acetylacetone peroxide (Percure AH, AL), 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane (Perhexa TMH), 1,1-di(t-hexyl peroxy)cyclohexane (Perhexa HC), 1,1-di(t-butylperoxy)-2-methylcyclohexane (Perhexa MC), 1,1-di(t-butylperoxy)cyclohexane (Perhexa C-80(S), Perhexa C-75(EB), Perhexa C(C), Perhexa C-40, Perhexa C-40MB(S)), 2,2-di(t-butylperoxy)butane (Perhexa 22), 4,4-di-(t-butylperoxy)butylpentanoate (Perhexa V, Perhexa V-40(F)), 2,2-di(4,4-Di-(t-butylperoxy)cyclohexyl)propane (Pertetra A), p-menthane hydroperoxide (Permenta H), diisopropylbenzene hydroperoxide (Percumyl P), 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H), cumene hydroperoxide (Percumyl H-80), t-butyl hydroperoxide (Perbutyl H-69), di(2-t-butylperoxyisopropyl)benzene (Perbutyl P, Perbutyl P-40, Peroximon F-40, Perbutyl P-40MB(K)), di-t-hexyl peroxide (Perhexyl D), diisobutyryl peroxide (Perloyl IB), di(3,5,5-trimethylhexanoyl) peroxide (Perloyl 355(S)), dilauroyl peroxide (Perloyl L), disuccinic acid peroxide (Perloyl SA), di-(3-methylbenzoyl) Dibenzoyl peroxide, benzoyl (3-methylbenzoyl) peroxide, and dibenzoyl peroxide mixture (Niper BMT-K40, Niper BMT-M), dibenzoyl peroxide (Niper BW, Niper BO, Niper FF, Niper BS, Niper E, Niper NS), di(4-methylbenzoyl) peroxide (Niper PMB), di-n-propyl peroxydicarbonate (Perroyl NPP-50M) ), diisopropyl peroxydicarbonate (Perloyl IPP-50, Perloyl IPP-27), di(4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP), di(2-ethylhexyl) peroxydicarbonate (Perloyl OPP), di-sec-butyl peroxydicarbonate (Perloyl SBP), cumyl peroxyneodecanoate (Percumyl ND, Percumyl ND-50E), 1,1,3,3-Tetramethylbutyl peroxyneodecanoate (Perocta ND, Perocta ND-50E), t-hexyl peroxyneodecanoate (Perhexyl ND, Perhexyl ND-50E), t-butyl peroxyneodecanoate (Perbutyl ND, Perbutyl ND-50E), t-butyl peroxyneoheptanoate (Perbutyl NHP), t-hexyl peroxypivalate (Perhexyl PV, Perhexyl PV-50E), t -butyl peroxypivalate (Perbutyl PV, Perbutyl PV-40E), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O), 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Perhexa 25 O), t-hexylperoxy-2-ethylhexanoate (Perhexyl O, Percure HO(N)), t-butylperoxy-2-ethylhexanoate (Perb Percure O), t-hexylperoxyisopropyl monocarbonate (Perhexyl I), t-butylperoxy-3,5,5-trimethylhexanoate (Perbutyl 355), t-butylperoxylaurate (Perbutyl L), t-butylperoxy-2-ethylhexyl monocarbonate (Perbutyl E), t-hexylperoxybenzoate (Perhexyl Z), t-butylperoxyacetate (Perbutyl A), a mixture of t-butylperoxy-3-methylbenzoate and t-butylperoxybenzoate (Perbutyl ZT), t-butylperoxybenzoate (Perbutyl Z), t-butylperoxyallyl monocarbonate (Peromer AC), 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone (BTTB-25), 2,3-dimethyl-2,3-diphenylbutane (Nofumer BC-90), and the like can be mentioned. Among these, dialkyl-type organic peroxides are preferred. 2,5-dimethyl-2,5-di(t-butylperoxy)hexane is particularly preferred. Generally, the type and amount of organic peroxide used are selected taking into consideration the amount of active -O-O-, decomposition temperature, etc.

[0427] In this case, the crosslinking aid that can be used may be any compound that has reactivity with peroxy radicals and polymer radicals, such as -CH=CH ２ , -CH ２ CH=CH ２ , -CF=CF ２ , -C(CF ３ ) = CF ２ , -C(CH ３ ) = CF ２ , -CF=CF(CF ３ ), -CF=CF(CH ３ ), -C(C ６ H ５ ) = CF ２ , -CF=CF(C ６ H ５ ), —CH═CF ２ , -CF=CHF, -C(CF ３ )=CHF, -CF=CH(CF ３ ), -CH=CF(CF ３ ) and other polyfunctional compounds having functional groups such as ("C" in each formula) ６ H ５ " represents a phenyl group). Specific examples include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N,N'-n-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, 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, triallyl phosphite, N,N-diallylacrylamide, and 1,6-divinyldodecafluorohexane.

[0428] Furthermore, examples of the crosslinking aid used together with the peroxide crosslinking agent include a crosslinking aid represented by the general formula (31): (Wherein, six R ３１ are each independently H, a halogen atom, or an optionally halogenated group having 1 to 5 carbon atoms which may contain an ether bond; Z ３１may also include compounds represented by a linear or branched alkylene group, cycloalkylene group, or (per)fluoropolyoxyalkylene group having 1 to 18 carbon atoms, which optionally contains a heteroatom and is optionally halogenated.

[0429] The compound represented by general formula (31) includes compounds represented by general formula (32): (wherein j is an integer of 2 to 10, preferably an integer of 4 to 8, and four R ３２ are each independently H, F, or an alkyl group or (per)fluoroalkyl group having 1 to 5 carbon atoms, a compound represented by general formula (33): (In the formula, Y ３１ are each independently F, Cl or H, and Y ３２ are each independently F, Cl, H or OR ３３ (where R ３３ is a branched or straight chain alkyl group which may be partially, substantially or completely fluorinated or chlorinated; Z ３３ is a divalent group having 2 to 10 carbon atoms, optionally fluorinated, optionally interrupted by ether linkages, preferably Z ３３ m is an integer of 3 to 5, -(CF ２ ) ｍ - group, and the compound represented by general formula (33) is preferably F ２ C=CF-O-(CF ２ ) ５ -O-CF=CF ２ a compound represented by general formula (34): (In the formula, Y ３１ , Y ３２ and Z ３３ is as described above, and R ３４ are each independently H, F, or an alkyl group or (per)fluoroalkyl group having 1 to 5 carbon atoms.

[0430] The crosslinking agent or the crosslinking aid used together with the peroxide crosslinking agent may be a crosslinking aid represented by the general formula (35):

[0431] (In the formula, R ３５ ~R ３７ are each independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group, and R ３５ ~R ３７ At least one of R is a fluorine atom or a group containing a fluorine atom. m is an integer of 1 to 5. When m is 2 or more, m R ３５ ~R ３７ may be the same or different. A hydrogen atom on the benzene ring may be substituted. When m is 1, it is preferable that the compound has two or more of the structure.

[0432] The compound having the structure represented by general formula (35) includes compounds having the structure represented by general formula (36):

[0433] (In the formula, R ３５ ~R ３７ is as defined above, p is an integer of 0 to 2, and n is an integer of 2 to 6.), a compound represented by general formula (37):

[0434] (In the formula, R ３５ ~R ３７ is as above. ３８ is a single bond, -SO ２ -, -O-, -S-, -CO-, a heteroatom-containing group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group. m is an integer of 1 to 5. These groups may be partially or completely fluorinated.

[0435] The heteroatom-containing group is not particularly limited as long as it is a divalent group containing a heteroatom, and examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a boron atom, and a phosphorus atom.

[0436] Examples of crosslinking agents used for polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

[0437] Examples of crosslinking agents used for polyamine crosslinking include polyamine compounds such as hexamethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate.

[0438] Examples of crosslinking agents used for triazine crosslinking include organic tin compounds such as tetraphenyltin and triphenyltin.

[0439] Examples of crosslinking agents used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include those represented by the general formula (41):

[0440]

[0441] (In the formula, R ４１ Ha-SO ２ -, -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms or a single bond, or

[0442]

[0443] and R ４２ and R ４３ One side is -NH ２ and the other is -NHR ４４ , -NH ２ , —OH or —SH, and R ４４ is a hydrogen atom, a fluorine atom or a monovalent organic group, and preferably R ４２ Ga-NH ２ And R ４３ Ga-NHR ４４ Preferred specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and preferred specific examples of the perfluoroalkylene group having 1 to 10 carbon atoms include:

[0444]

[0445] These compounds are known as examples of bisdiaminophenyl compounds in JP-B 2-59177, JP-A 8-120146, etc.), bisaminophenol-based crosslinking agents, bisaminothiophenol-based crosslinking agents represented by general formula (42):

[0446] (R ４１ As mentioned above, R ４５ are each independently any of the following groups:

[0447] Bisamidrazone crosslinking agents represented by general formula (43):

[0448]

[0449] (wherein, Rf ４１ is a perfluoroalkylene group having 1 to 10 carbon atoms), or an amidrazone crosslinking agent represented by the general formula (44):

[0450]

[0451] (wherein n is an integer of 1 to 10), a bisamidoxime crosslinking agent represented by the general formula (45): HN=CR ４５ R ４６ (In the formula, R ４５ , H, NH ２ , and N.H.R. ４７ and R ４６ is Ph, SO ２ H, N.R. ４８ R ４９ , 2-pyridine, and CH ２ CONH ２ and R ４７ Ph, NH ２ and CN, R ４８ is H, NHPh, CH ２ CONH ２ , a linear alkyl group having 1 to 8 carbon atoms, and a branched alkyl group having 1 to 8 carbon atoms; and R ４９ is Ph, COOC (CH ３ ) ３ , N.H.２ , C.H. ２ COOH, CSNH ２ , CNHNH ３ ＋ Cl － , p-phenylCN, and COPh). These bisaminophenol-based crosslinking agents, bisaminothiophenol-based crosslinking agents, and bisdiaminophenyl-based crosslinking agents have conventionally been used in crosslinking systems using cyano groups as crosslinking points, but they also react with carboxyl groups and alkoxycarbonyl groups to form oxazole rings, thiazole rings, and imidazole rings, thereby giving crosslinked products.

[0452] The crosslinking agent may be a compound represented by the general formula (46): X ４１ - (CH ２ ) ｎ -R ５０ - (CH ２ ) ｍ -X ４１ (In the formula, X ４１ each independently represents an alkyne group, a cyano group, or Y ４１ Ｐ N ３ (Y ４１ SO, SO ２ , C ６ H ４ or CO, and p is 0 or 1, n and m are independently integers of 1 to 4, and R ５０The crosslinking agent may be selected from the group consisting of: i) a fluoroalkylene group having 3 to 10 carbon atoms, ii) a fluoroalkoxylene group having 3 to 10 carbon atoms, iii) a substituted arylene group, iv) an oligomer containing copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether), v) an oligomer containing copolymerized units of vinylidene fluoride and hexafluoropropylene, vi) an oligomer containing copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and vii) an oligomer containing copolymerized units of tetrafluoroethylene and a hydrocarbon olefin. This crosslinking agent is preferably used together with a perfluoroelastomer having a cyano group, an azide group, a sulfonyl azide group, a carbonyl azide group, or an alkyne group. For example, the cyano group of the perfluoroelastomer reacts with the azide group of the crosslinking agent to form a tetrazole ring, resulting in a crosslinked product.

[0453] Particularly preferred crosslinking agents include compounds having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, or compounds represented by the general formula (47):

[0454]

[0455] (In the formula, R ４１ , R ４２ and R ４３are as described above), and specific examples thereof include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (general name: bis(aminophenol) AF), 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane, tetraaminobenzene, bis-3,4-diaminophenylmethane, bis-3,4-diaminophenyl ether, 2,2-bis(3,4-diaminophenyl)hexafluoropropane, 2,2-bis[3-amino-4-(N-phenylamino)phenyl] [3-amino-4-(N-methylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-ethylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-propylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-perfluorophenylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-benzylamino)phenyl]hexafluoropropane, and the like.

[0456] Among these, 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane (AFTA-Ph) is preferred as the crosslinking agent from the viewpoints of heat resistance, steam resistance, amine resistance, and good crosslinking properties.

[0457] The content of the crosslinking agent is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the fluororubber (perfluoroelastomer).

[0458] In one embodiment of the crosslinkable composition of the present disclosure, the fluororubber contains a perfluoroelastomer having an iodine atom or a bromine atom.

[0459] When the crosslinkable composition of the present disclosure contains a perfluoroelastomer having an iodine atom or a bromine atom, a crosslinked product having particularly small compression set can be obtained because the content of polymer (I) in the crosslinkable composition of the present disclosure is significantly reduced.

[0460] The content of polymer (I) in the crosslinkable composition of the present disclosure is preferably 0.0001 to 1.0% by mass relative to the perfluoroelastomer having iodine atoms or bromine atoms. Since the compression set of the resulting crosslinked product is further reduced, the content of polymer (I) relative to the perfluoroelastomer having iodine atoms or bromine atoms is more preferably 0.001% by mass or more, even more preferably 0.005% by mass or more, particularly preferably 0.01% by mass or more, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less. The content of polymer (I) relative to the perfluoroelastomer having iodine atoms or bromine atoms may be less than 0.1% by mass, 0.05% by mass or less, or 0.02% by mass or less.

[0461] When the crosslinkable composition of the present disclosure contains a perfluoroelastomer having an iodine atom or a bromine atom, the crosslinkable composition preferably contains an organic peroxide as a crosslinking agent. As the organic peroxide, the above-mentioned organic peroxides can be suitably used.

[0462] When the crosslinkable composition of the present disclosure contains a perfluoroelastomer having an iodine atom or a bromine atom, it preferably contains a crosslinking aid, and more preferably contains an organic peroxide and a crosslinking aid. As the crosslinking aid, those described above can be suitably used.

[0463] Next, the perfluoroelastomer having an iodine atom or a bromine atom will be described.

[0464] The perfluoroelastomer having an iodine atom or a bromine atom preferably has an iodine atom or a bromine atom at the end of the main chain and / or in a side chain, and may have both an iodine atom and a bromine atom.

[0465] The perfluoroelastomer having an iodine atom or a bromine atom is preferably at least one selected from the group consisting of perfluoroelastomers containing a monomer unit having an iodine atom or a bromine atom, perfluoroelastomers having an iodine atom or a bromine atom at the main chain terminal, and perfluoroelastomers having an iodine atom or a bromine atom at the main chain terminal and containing a monomer unit having an iodine atom or a bromine atom.

[0466] The monomer having an iodine atom or a bromine atom includes a monomer represented by the formula: CX ４ ２ =CX ５ R ｆ ２ -X (wherein, X ４ , X ５ are each independently H, F or an alkyl group having 1 to 5 carbon atoms, and R ｆ ２ is a linear or branched alkylene or oxyalkylene group which may have one or more ether-bonded oxygen atoms and which may have an aromatic ring, and in which some or all of the hydrogen atoms may be substituted with fluorine atoms, and X is an iodine atom or a bromine atom).

[0467] Examples of the monomer having an iodine atom or a bromine atom include a monomer represented by the formula: CX １６ ２ =CX １６ -Rf １６ CHR １６ X (wherein, X １６ are each independently a hydrogen atom, a fluorine atom, or CH ３ , Rf １６ represents a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R １６ is a hydrogen atom or CH ３ , X is an iodine atom or a bromine atom), １６ ２ =CX １６ -Rf １７ X (wherein, X １６are each independently a hydrogen atom, a fluorine atom, or CH ３ , Rf １７ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, and X is an iodine atom or a bromine atom), ２ = CFO (CF ２ CF (CF ３ ) O) ｍ (CF ２ ) ｎ -X (wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X is an iodine atom, a bromine atom, or -CH ２ I), a fluoromonomer represented by the formula: CH ２ =CFCF ２ O(CF(CF ３ )CF ２ O) ｍ (CF (CF ３ )) ｎ -X (wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X is an iodine atom or a bromine atom), and the like. These can be used alone or in any combination.

[0468] X １６ is preferably a fluorine atom. １６ and Rf １７ is preferably a perfluoroalkylene group having 1 to 5 carbon atoms. １６ is preferably a hydrogen atom.

[0469] Examples of the monomer having an iodine atom or a bromine atom include CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CH ２ I, CF ２ = CFOCF ２ CF ２ CH ２ I, and CH ２ = CHCF ２ CF ２I is preferred, and CF ２ = CFOCF ２ CF ２ CH ２ I is more preferred.

[0470] The perfluoroelastomer having an iodine atom or a bromine atom at the end of the main chain can be produced by using an iodine compound or a bromine compound as a chain transfer agent when producing the perfluoroelastomer by polymerizing a monomer.The polymerization method using an iodine compound or a bromine compound can be, for example, a method of carrying out emulsion polymerization in an aqueous medium under pressure in the presence of an iodine compound or a bromine compound in a substantially oxygen-free state (iodine transfer polymerization method).Typical examples of the iodine compound or the bromine compound to be used include, for example, those represented by the general formula: R ２１ I ｘ Br ｙ (wherein x and y are each an integer of 0 to 2 and satisfy 1≦x+y≦2; R ２１ is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).

[0471] Examples of iodine compounds and bromine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF ２ Br ２ , BrCF ２ CF ２ Br, CF ３ CFBrCF ２ Br, CFClBr ２ , BrCF ２CFClBr, CFBrClCFClBr, BrCF ２ CF ２ CF ２ Br, BrCF ２ CFBrOCF ３ , 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted benzene, and (2-iodoethyl)- and (2-bromoethyl)-substituted benzenes. These compounds may be used alone or in combination with one another.

[0472] Among these, it is preferable to use 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane in terms of polymerization reactivity, crosslinking reactivity, availability, and the like.

[0473] The iodine atom and bromine atom content of the iodine atom or bromine atom-containing perfluoroelastomer is preferably 0.001 to 10% by mass, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and more preferably 5% by mass or less. If the iodine atom and bromine atom content is too low, the haze value will be large, and a crosslinked product exhibiting excellent transparency may not be obtained. The iodine atom and bromine atom content can be measured by elemental analysis.

[0474] As the perfluoroelastomer having iodine atoms or bromine atoms, at least one selected from the group consisting of perfluoroelastomers having iodine atoms or bromine atoms containing TFE units, such as TFE / fluoromonomer copolymers represented by general formula (160), (130) or (140), and TFE / fluoromonomer copolymers represented by general formula (160), (130) or (140) / monomer copolymers having iodine atoms or bromine atoms is preferred.

[0475] When the perfluoroelastomer having iodine atoms or bromine atoms is a TFE / perfluoro(methyl vinyl ether) (PMVE) copolymer, the composition (mol %) of the perfluoroelastomer having iodine atoms or bromine atoms is preferably 45-90 / 10-55, more preferably 55-80 / 20-45, even more preferably 55-70 / 30-45, and most preferably 56-69.5 / 30.5-44.

[0476] When the perfluoroelastomer having iodine atoms or bromine atoms is a copolymer of TFE / PMVE / monomer having iodine atoms or bromine atoms, the composition (mol %) of the perfluoroelastomer having iodine atoms or bromine atoms is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4, more preferably 55 to 77.9 / 20 to 49.9 / 0.01 to 3.5, even more preferably 55 to 69.8 / 30 to 44.8 / 0.03 to 3.0, and most preferably 55.3 to 69.5 / 30.3 to 44.5 / 0.05 to 2.5.

[0477] When the perfluoroelastomer having iodine atoms or bromine atoms is a copolymer of TFE / fluoromonomer having 4 to 12 carbon atoms and represented by general formula (160), (130) or (140), the composition (mol%) of the perfluoroelastomer having iodine atoms or bromine atoms is preferably 50 to 90 / 10 to 50, more preferably 60 to 88 / 12 to 40, even more preferably 65 to 85 / 15 to 35, and most preferably 66 to 84 / 16 to 34.

[0478] When the perfluoroelastomer having iodine or bromine atoms is a copolymer of TFE / fluoromonomer having 4 to 12 carbon atoms represented by the general formula (160), (130) or (140) / monomer having iodine or bromine atoms, the composition (mol%) of the perfluoroelastomer having iodine or bromine atoms is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4, more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3.0, and most preferably 66 to 84.3 / 15.5 to 33.8 / 0.2 to 2.0. Outside these composition ranges, the properties of the rubber elastic body are lost and tend to become similar to those of a resin.

[0479] The perfluoroelastomer having an iodine atom or a bromine atom is more preferably at least one selected from the group consisting of TFE / perfluorovinyl ether copolymer represented by general formula (140), TFE / fluoromonomer copolymer represented by general formula (140) / monomer copolymer having an iodine atom or a bromine atom, TFE / fluoromonomer copolymer represented by general formula (160), and TFE / fluoromonomer copolymer represented by general formula (160) / monomer copolymer having an iodine atom or a bromine atom.

[0480] The perfluoroelastomer having an iodine atom or a bromine atom has a glass transition temperature of preferably −70° C. or higher, more preferably −60° C. or higher, and even more preferably −50° C. or higher, from the viewpoint of excellent compression set properties at high temperatures. Furthermore, from the viewpoint of good cold resistance, the glass transition temperature is preferably 5° C. or lower, more preferably 0° C. or lower, and even more preferably −3° C. or lower.

[0481] The glass transition temperature can be determined by obtaining a DSC curve using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo) by heating 10 mg of a sample at a rate of 10°C / min, and by determining the temperature as the midpoint between two intersections of an extension of the baseline of the DSC curve before and after the second-order transition and a tangent to the inflection point of the DSC curve.

[0482] In terms of good heat resistance, the perfluoroelastomer having an iodine atom or a bromine atom preferably has a Mooney viscosity ML(1+10) at 100°C of 10 or more, more preferably 20 or more, and even more preferably 25 or more. In terms of good processability, the Mooney viscosity ML(1+10) is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0483] The Mooney viscosity can be measured at 100° C. in accordance with JIS K6300 using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

[0484] In one embodiment of the crosslinkable composition of the present disclosure, a perfluoroelastomer having a cyano group is contained as the fluororubber.

[0485] When the crosslinkable composition of the present disclosure contains a perfluoroelastomer having a cyano group, crosslinking can be achieved at a high crosslinking rate, because the content of the polymer (I) in the crosslinkable composition of the present disclosure is significantly reduced.

[0486] The content of polymer (I) in the crosslinkable composition of the present disclosure is preferably 0.0001 to 1.0% by mass relative to the perfluoroelastomer having a cyano group. Since the crosslinking rate of the crosslinkable composition is further increased, the content of polymer (I) relative to the perfluoroelastomer having a cyano group is more preferably 0.001% by mass or more, even more preferably 0.005% by mass or more, particularly preferably 0.01% by mass or more, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less. The content of polymer (I) relative to the perfluoroelastomer having a cyano group may be less than 0.1% by mass, 0.05% by mass or less, or 0.02% by mass or less.

[0487] When the crosslinkable composition of the present disclosure contains a perfluoroelastomer having a cyano group, the crosslinkable composition may contain an inorganic nitride, an organotin compound, a compound that generates ammonia, a compound having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, and a compound represented by the general formula (47): (In the formula, R ４１ , R ４２ and R ４３ As the inorganic nitride, the organic tin compound, the ammonia-generating compound, and the crosslinking agent therefor, the above-mentioned compounds can be suitably used.

[0488] Next, the perfluoroelastomer having a cyano group will be described.

[0489] Perfluoroelastomers having a cyano group (-CN group) can be crosslinked by forming a triazine ring through cyclotrimerization of the cyano group, and can impart excellent compression set properties and heat resistance to the crosslinked product.

[0490] The perfluoroelastomer having a cyano group preferably has a cyano group (-CN group) at the end of the main chain and / or in a side chain.

[0491] The perfluoroelastomer having a cyano group preferably contains a monomer unit having a cyano group. The monomer having a cyano group is preferably a monomer represented by the formula: CX ４ ２ =CX ５ R ｆ ２ -CN (wherein, X ４ , X ５ are each independently H, F or an alkyl group having 1 to 5 carbon atoms, and R ｆ ２ is a linear or branched alkylene or oxyalkylene group which may have one or more ether-bonded oxygen atoms, which may have an aromatic ring, and in which some or all of the hydrogen atoms may be substituted with fluorine atoms).

[0492] Examples of the monomer having a cyano group include a monomer represented by the formula: CY １ ２ =CY １ (CF ２ ) ｎ —CN (wherein Y １ are each independently a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8. ２ =CFCF ２ Rf ８ -CN (wherein, Rf ８ Ha-(OCF ２ ) ｎ - or - (OCF (CF ３ )) ｎ -, and n is an integer from 0 to 5) Formula: CF ２ =CFCF ２ (OCF (CF ３ )CF ２ ) ｍ (OCH ２ CF ２ CF ２ ) ｎ OCH ２ CF ２ -CN (wherein m is an integer of 0 to 5, and n is an integer of 0 to 5) Formula: CF ２ =CFCF ２ (OCH ２ CF ２ CF ２ ) ｍ (OCF (CF ３ )CF ２ ) ｎ OCF (CF ３ )-CN (wherein m is an integer of 0 to 5, and n is an integer of 0 to 5) Formula: CF ２ =CF(OCF ２ CF (CF ３ )) ｍ O (CF ２ ) ｎ -CN (wherein m is an integer of 0 to 5, and n is an integer of 1 to 8) Formula: CF ２ =CF(OCF ２ CF (CF ３ )) ｍ -CN (wherein m is an integer of 1 to 5) Formula: CF ２ = CFOCF ２ (CF (CF３ ) OCF ２ ) ｎ CF(-CN)CF ３ (wherein n is an integer of 1 to 4) Formula: CF ２ = CFO (CF ２ ) ｎ OCF (CF ３ )-CN (wherein n is an integer of 2 to 5) Formula: CF ２ = CFO (CF ２ ) ｎ -(C ６ H ４ )-CN (wherein n is an integer from 1 to 6) Formula: CF ２ =CF(OCF ２ CF (CF ３ )) ｎ OCF ２ CF (CF ３ )-CN (wherein n is an integer of 1 to 2) Formula: CH ２ =CFCF ２ O(CF(CF ３ )CF ２ O) ｎ CF (CF ３ )-CN (wherein n is an integer from 0 to 5) Formula: CF ２ = CFO (CF ２ CF (CF ３ ) O) ｍ (CF ２ ) ｎ —CN (wherein m is an integer of 0 to 5, and n is an integer of 1 to 3) Formula: CH ２ =CFCF ２ OCF (CF ３ ) OCF (CF ３ )-CN Formula: CH ２ =CFCF ２ OCH ２ CF ２ -CN Formula: CF ２ = CFO (CF ２ CF (CF ３ ) O) ｍ CF ２ CF (CF ３ )-CN (wherein m is an integer of 0 or more) Formula: CF ２ = CFOCF(CF ３ )CF ２O (CF ２ ) ｎ -CN (wherein n is an integer of 1 or more) Formula: CF ２ = CFOCF ２ OCF ２ CF (CF ３ ) OCF ２ These may be used alone or in any combination.

[0493] Among the monomers having a cyano group (-CN group), there are those represented by the formula: CF ２ =CF(OCF ２ CF (CF ３ )) ｍ O (CF ２ ) ｎ -CN (wherein m is an integer of 0 to 5, and n is an integer of 1 to 8) is preferred, and CF ２ = CFOCF ２ CF (CF ３ ) OCF ２ CF ２ CN is more preferred.

[0494] Examples of perfluoroelastomers having a cyano group include copolymers of TFE / fluoromonomers represented by general formula (160), (130) or (140) / monomers having a cyano group. In this case, from the viewpoint of good crosslinking properties and heat resistance, the content of the monomer units having a cyano group may be 0.1 to 5 mol%, or may be 0.3 to 3 mol%, based on the total amount of TFE units and fluoromonomer units represented by general formula (160), (130) or (140).

[0495] When the perfluoroelastomer having a cyano group is a copolymer of TFE / perfluoro(methyl vinyl ether) (PMVE) / monomer having a cyano group, the composition (mol %) of the perfluoroelastomer having a cyano group is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4, more preferably 55 to 77.9 / 20 to 49.9 / 0.1 to 3.5, even more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3, and most preferably 55.3 to 69.5 / 30.3 to 44.5 / 0.2 to 2.8.

[0496] When the perfluoroelastomer having a cyano group is a copolymer of TFE / fluoromonomer having 4 to 12 carbon atoms represented by the general formula (160), (130) or (140) / monomer having a cyano group, the composition (mol%) of the perfluoroelastomer having a cyano group is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4, more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3, and most preferably 66 to 84.3 / 15.5 to 33.8 / 0.2 to 2.8. Outside these composition ranges, the properties of the rubber elastic body are lost and tend to become similar to those of a resin.

[0497] The perfluoroelastomer having a cyano group is preferably at least one selected from the group consisting of a copolymer of TFE / fluoromonomer represented by general formula (140) / monomer having a cyano group, and a copolymer of TFE / fluoromonomer represented by general formula (160) / monomer having a cyano group.

[0498] The perfluoroelastomer having a cyano group may have a polar end group. By end group is meant any group present on the main chain of the polymer or on any long or short end that may be present. Polar end groups include carboxylate (-COO － ) group and sulfonate (-OSO ３ － ) groups, and alcohol (-CH ２ OH), acyl fluoride (-COF), amide (-CONH２ The polar end groups can be introduced into the elastomer by using an inorganic peroxide or the like as a polymerization initiator when producing the perfluoroelastomer by polymerizing the monomer. The presence or absence of the polar end groups can be confirmed by Fourier transform infrared spectroscopy (FTIR).

[0499] The cyano group-containing perfluoroelastomer preferably has a glass transition temperature of −70° C. or higher, more preferably −60° C. or higher, and even more preferably −50° C. or higher, from the viewpoint of excellent compression set properties at high temperatures. Furthermore, from the viewpoint of good cold resistance, the glass transition temperature is preferably 5° C. or lower, more preferably 0° C. or lower, and even more preferably −3° C. or lower.

[0500] The glass transition temperature can be determined by obtaining a DSC curve using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo) by heating 10 mg of a sample at a rate of 10°C / min, and by determining the temperature as the midpoint between two intersections of an extension of the baseline of the DSC curve before and after the second-order transition and a tangent to the inflection point of the DSC curve.

[0501] In terms of good heat resistance, the cyano group-containing perfluoroelastomer preferably has a Mooney viscosity ML(1+20) at 170°C of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In terms of good processability, the Mooney viscosity ML(1+20) is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

[0502] The Mooney viscosity can be measured at 170° C. in accordance with JIS K6300 using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

[0503] The crosslinkable composition may contain a filler.

[0504] Examples of the filler include organic fillers, and from the viewpoints of heat resistance and plasma resistance (low particle generation and low weight loss rate upon plasma irradiation), organic pigments; imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide; and ketone-based engineering plastics such as polyetheretherketone (PEEK) and polyetherketone (PEK) are preferred, with organic pigments being particularly preferred.

[0505] Examples of organic pigments include condensed azo pigments, isoindolinone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and anthraquinone pigments. Among these, quinacridone pigments, diketopyrrolopyrrole pigments, and anthraquinone pigments are preferred, with quinacridone pigments being more preferred, because they have excellent heat resistance and chemical resistance and have little effect on the properties of the crosslinked product.

[0506] Furthermore, it may contain a general filler.The general filler may include: an organic filler made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyoxybenzoate, polytetrafluoroethylene powder, etc.; a metal oxide filler such as aluminum oxide, silicon oxide, yttrium oxide, titanium oxide, etc.; a metal carbide filler such as silicon carbide, aluminum carbide, etc., a metal nitride filler such as silicon nitride, aluminum nitride, etc.; an inorganic filler such as aluminum fluoride, carbon fluoride, barium sulfate, carbon black, silica, clay, talc, etc.

[0507] Among these, carbon black, aluminum oxide, silicon oxide, yttrium oxide, silicon nitride, polyimide, carbon fluoride, and silicon carbide are preferred in terms of their shielding effect against various plasmas.

[0508] In addition, inorganic fillers and organic fillers may be blended alone or in combination of two or more.

[0509] The content of the filler in the crosslinkable composition is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the fluororubber (perfluoroelastomer).

[0510] In particular, in fields where high purity and non-staining properties are not required, ordinary additives that are compounded in perfluoroelastomers, such as processing aids, plasticizers, colorants, etc., may be compounded as needed, and one or more commonly used crosslinking agents or crosslinking aids different from those mentioned above may also be compounded.

[0511] The crosslinkable composition may contain an organic basic compound. Examples of the organic basic compound include a compound represented by the formula: CH ３ (CH ２ ) １７ -NH ２ Octadecylamine of formula: H ２ NC(O)-(CH ２ ) １１ -CH=CH-(CH ２ ) ７ CH ３ Erucamide of formula: H ２ NC(O)-(CH ２ ) ７ -CH=CH-(CH ２ ) ７ CH ３ Oleamide of formula: H ２ N-(CH ２ ) ６ -NH ２ Hexamethylenediamine of the formula: Examples of suitable cyclopentadiene compounds include 1,8-diazabicycloundec-7-ene (DBU) of the formula:

[0512] The crosslinkable composition can be prepared by mixing the above-mentioned components using a conventional polymer processing machine, such as an open roll, a Banbury mixer, a kneader, etc. Alternatively, it can also be prepared by a method using an internal mixer.

[0513] A crosslinked product can be obtained by crosslinking the above-mentioned crosslinkable composition.

[0514] The crosslinking can be carried out in the order of primary crosslinking and secondary crosslinking. The primary crosslinking is preferably carried out at 150 to 250°C for 5 to 120 minutes, and more preferably at 160 to 200°C for 5 to 60 minutes. Any known crosslinking means may be used for the crosslinking, and examples thereof include press crosslinking.

[0515] The secondary crosslinking is preferably carried out at 150 to 320° C. for 2 to 48 hours, more preferably at 180 to 310° C. for 3 to 24 hours. Any known crosslinking means may be used as the crosslinking means, and examples thereof include oven crosslinking.

[0516] The crosslinkable composition may be molded to obtain a preform, and then crosslinked to obtain a crosslinked product (molded article). The method for molding the crosslinkable composition to obtain a preform may be a conventional method, and can be performed by known methods such as a method of heating and compressing in a mold, a method of forcing into a heated mold, or a method of extruding with an extruder. In the case of extruded products such as hoses and electric wires, a crosslinked product can be obtained by performing heat crosslinking with steam or the like after extrusion.

[0517] The crosslinked product of the present disclosure can be suitably used as a sealing material for semiconductor manufacturing equipment that requires heat resistance, particularly for semiconductor manufacturing equipment that is exposed to high-density plasma. Examples of such sealing materials include O-rings, square rings, gaskets, packing, oil seals, bearing seals, and lip seals.

[0518] In addition, it can be used for various polymer products used in semiconductor manufacturing equipment, such as diaphragms, tubes, hoses, various rubber rolls, belts, etc. It can also be used as a coating material or a lining material.

[0519] It should be noted that the semiconductor manufacturing equipment referred to in this disclosure is not limited to equipment specifically for manufacturing semiconductors, but broadly includes all manufacturing equipment used in the semiconductor field that requires a high degree of cleanliness, such as equipment for manufacturing liquid crystal panels and plasma panels, and examples thereof include the following:

[0520] (1) Etching equipment Dry etching equipment Plasma etching equipment Reactive ion etching equipment Reactive ion beam etching equipment Sputter etching equipment Ion beam etching equipment Wet etching equipment Ashing equipment (2) Cleaning equipment Dry etching cleaning equipment UV / O ３ Cleaning equipment Ion beam cleaning equipment Laser beam cleaning equipment Plasma cleaning equipment Gas etching cleaning equipment Extraction cleaning equipment Soxhlet extraction cleaning equipment High temperature and high pressure extraction cleaning equipment Microwave extraction cleaning equipment Supercritical extraction cleaning equipment (3) Exposure equipment Stepper Coater / Developer (4) Polishing equipment CMP equipment (5) Film formation equipment CVD equipment Sputtering equipment (6) Diffusion / ion implantation equipment Oxidation diffusion equipment Ion implantation equipment

[0521] The crosslinked product of the present disclosure exhibits excellent performance as a sealing material for, for example, a CVD apparatus, a plasma etching apparatus, a reactive ion etching apparatus, an ashing apparatus, or an excimer laser exposure apparatus.

[0522] Furthermore, the crosslinked product of the present disclosure has excellent heat resistance, oil resistance, amine resistance, chemical resistance, and cold resistance, and is generally used in areas where it comes into contact with other materials and slides, where it seals or seals other materials or substances, or where the purpose is vibration damping or soundproofing, and can be used as various parts in various fields such as the automobile industry, the aircraft industry, and the semiconductor industry. Examples of fields in which it is used include semiconductor-related fields, automobiles, aircraft, space and rockets, ships, chemical plants, pharmaceuticals, and other fields, photographic fields such as developing machines, printing fields such as printing machines, painting fields such as painting equipment, analytical instruments, analytical and physicochemical machinery fields such as meters, food equipment including food plant equipment and household goods, food beverage manufacturing equipment, pharmaceutical manufacturing equipment, medical parts, chemical transport equipment, nuclear power plant equipment, steel fields such as iron plate processing equipment, general industry, electricity, fuel cells, electronic components, optical equipment parts, space equipment parts, petrochemical plant equipment, oil, gas, and other energy resource exploration and mining equipment parts, petroleum refining, and petroleum transportation equipment parts.

[0523] Examples of use forms of the crosslinked product of the present disclosure include various sealing materials and packings such as rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, and barrel seals. As a sealing material, it can be used in applications requiring heat resistance, solvent resistance, chemical resistance, and non-stickiness. It can also be used as a tube, hose, roll, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve bodies, chemical-resistant coating materials, laminating materials, lining materials, and the like. The cross-sectional shape of the rings, packings, and seals may be various shapes, specifically, for example, square, O-shaped, ferrule-shaped, or irregular shapes such as D-shaped, L-shaped, T-shaped, V-shaped, X-shaped, and Y-shaped.

[0524] In the semiconductor-related fields, the present invention can be used, for example, in 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. Examples of such equipment include 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, sputter 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, polishing equipment, film formation equipment, dry etching cleaning equipment, UV / O ３Cleaning equipment, ion beam cleaning equipment, laser beam cleaning equipment, plasma cleaning equipment, gas etching cleaning equipment, extraction 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., steppers, coater developers, CMP equipment, excimer laser exposure machines, chemical liquid piping, gas piping, NF ３ Plasma treatment, O ２ Examples of such equipment include equipment for performing plasma treatment such as plasma treatment and fluorine plasma treatment, heat treatment film formation equipment, wafer transport equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp annealing processes, and equipment used in reflow processes.

[0525] Specific uses in the semiconductor-related field include various sealing materials such as O-rings and gaskets for gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, and pumps; various sealing materials such as O-rings for resist developer and stripper solutions, hoses and tubes; linings and coatings for resist developer tanks, stripper tanks, wafer cleaning solution tanks, and wet etching tanks; pump diaphragms; rolls for transporting wafers; hose tubes for wafer cleaning solutions; sealing materials for clean facilities such as sealants for clean facilities in clean rooms and the like; sealing materials for storage cabinets for storing semiconductor manufacturing equipment and devices such as wafers; and diaphragms for transporting chemical solutions used in the process of manufacturing semiconductors.

[0526] In the above-mentioned automotive field, the crosslinked product can be used in the engine body, main drive system, valve train system, lubrication and cooling system, fuel system, intake and exhaust system, drivetrain transmission system, chassis steering system, brake system, and electrical components such as basic electrical components, control system electrical components, and equipment electrical components. The above-mentioned automotive field also includes motorcycles. In the above-mentioned engine body and its peripheral devices, the crosslinked product of the present disclosure can be used for various sealing materials that require heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance. Examples of such sealing materials include gaskets, shaft seals, valve stem seals, and other seals; non-contact or contact packings such as self-sealing packings, piston rings, split-ring packings, mechanical seals, and oil seals; bellows, diaphragms, hoses, and tubes; as well as electric wires, cushioning materials, vibration-proofing materials, and various sealing materials used in belt-type automatic transmissions.

[0527] Specific uses in the above fuel systems include O-rings used in fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel tube bodies, fuel tube connectors, injectors, etc.; seals used in intake system manifolds, fuel filters, pressure regulating valves, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sender units, fuel injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid sub-assemblies, fuel cut valves, etc.; canister purge solenoid valve seals, onboard refueling vapor recovery (ORVR) valve seals, fuel pump oil seals, fuel sender seals, fuel tank rollover valve seals, filler seals, injector seals, filler cap seals, filler cap valves, etc. Seals; hoses such as fuel hoses, fuel supply hoses, fuel return hoses, vapor (evaporative) hoses, vent (breather) hoses, filler hoses, filler neck hoses, hoses inside fuel tanks (in-tank hoses), carburetor control hoses, fuel inlet hoses, and fuel breather hoses; gaskets used in fuel filters and fuel line connector systems, and flange gaskets used in carburetors; line materials such as vapor recovery lines, fuel feed lines, and vapor / ORVR lines; diaphragms used in canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, composite air control devices (CACs), pulsation dampers, canisters, autococks, and pressure regulator diaphragms for fuel injection systems; fuel pump valves, carburetor needle valves, rollover check valves, check valves; vents (breathers), and tubes used inside fuel tanks; tank packings for fuel tanks, etc., and packings for carburetor acceleration pump pistons;Examples include fuel sender vibration isolation parts for fuel tanks; O-rings and diaphragms for controlling fuel pressure; accelerator pump cups; in-tank fuel pump mounts; injector cushion rings for fuel injection systems; injector seal rings; carburetor needle valve core valves; carburetor accelerator pump pistons; valve seats for compound air control systems (CAC); fuel tank bodies; and sealing parts for solenoid valves.

[0528] Specific uses in the above-mentioned brake systems include diaphragms used in master bags, hydraulic brake hose air brakes, brake chambers of air brakes, etc.; hoses used in brake hoses, brake oil hoses, vacuum brake hoses, etc.; various sealing materials such as oil seals, O-rings, packing, and brake piston seals; atmospheric valves and vacuum valves for master bags, and check valves for brake valves; piston cups (rubber cups) and brake cups for master cylinders; boots for master cylinders and vacuum boosters of hydraulic brakes, wheel cylinders of hydraulic brakes, and O-rings and grommets for anti-lock braking systems (ABS).

[0529] Specific uses in the above basic electrical components include insulators and sheaths for electrical wires (harnesses), tubes for harness exterior components, and grommets for connectors. Specific uses in control system electrical components include coating materials for various sensor wires. Specific uses in the above equipment electrical components include O-rings and packings for car air conditioners, cooler hoses, high-pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug boots for direct ignition, and distributor diaphragms. It can also be used to bond electrical components.

[0530] Specific uses in the intake and exhaust systems include packings used in intake manifolds, exhaust manifolds, etc., and throttle body packings for throttles; diaphragms used in EGR (exhaust gas recirculation), pressure control (BPT), wastegates, turbo wastegates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc.; EGR (exhaust gas recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo oil hoses (return), turbo air hoses, intake ... Examples of such hoses include intercooler hoses, turbocharger hoses, hoses connected to the compressor of a turbo engine equipped with an intercooler, exhaust gas hoses, air intake hoses, turbo hoses, DPF (diesel particulate filter) sensor hoses, etc.; air ducts and turbo air ducts; intake manifold gaskets; EGR sealing materials, afterburn prevention valve seats for AB valves, turbine shaft seals (for turbochargers, etc.), and sealing members used in grooved parts such as rocker covers and air intake manifolds used in automobile engines.

[0531] In addition, the present invention can be used in exhaust gas control parts such as seals used in vapor recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., seals for solenoid armatures in vapor recovery and vapor canisters, and intake system manifold gaskets. In diesel engine parts, the present invention can be used as O-ring seals for direct injection injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, and boost compensator diaphragms. The present invention can also be used in O-rings, seals, hoses, tubes, and diaphragms used in urea SCR systems, as well as the urea water tank body and seals for the urea water tank in urea SCR systems.

[0532] Specific examples of applications in the transmission system include transmission-related bearing seals, oil seals, O-rings, packing, and torque converter hoses. Examples also include transmission oil seals, AT transmission oil hoses, ATF hoses, O-rings, and packing. Transmissions include automatic transmissions (ATs), manual transmissions (MTs), continuously variable transmissions (CVTs), and dual clutch transmissions (DCTs). Other examples include oil seals, gaskets, O-rings, and packing for manual or automatic transmissions, oil seals, gaskets, O-rings, and packing for continuously variable transmissions (belt or toroidal), as well as packing for ATF linear solenoids, oil hoses for manual transmissions, ATF hoses for automatic transmissions, and CVTF hoses for continuously variable transmissions (belt or toroidal). Specific examples of applications in the steering system include power steering oil hoses and high-pressure power steering hoses.

[0533] Examples of applications in the engine body of an automobile engine include gaskets such as cylinder head gaskets, cylinder head cover gaskets, oil pan packings, and general gaskets; seals such as O-rings, packings, and timing belt cover gaskets; hoses such as control hoses; vibration-isolating rubber for engine mounts; control valve diaphragms; and camshaft oil seals. In the main driving system of an automobile engine, they can be used for shaft seals such as crankshaft seals and camshaft seals. In the valve driving system of an automobile engine, they can be used for valve stem oil seals for engine valves and valve seats for butterfly valves. In the lubrication and cooling system of an automobile engine, they can be used for engine oil cooler hoses, oil return hoses, and seal gaskets for engine oil coolers, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, and vacuum pump oil hoses for vacuum pumps, as well as radiator hoses, radiator tanks, oil pressure diaphragms, and fan coupling seals.

[0534] Thus, specific examples of uses in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitrogen oxide (NOx) sensor seals, nitrogen oxide (NOx) sensor bushings, sulfur oxide sensor seals, temperature sensor seals, temperature sensor bushings, diesel particle filter sensor seals, diesel particle filter sensor bushings, injector O-rings, injector packings, fuel pump O-rings and diaphragms, gearbox seals, power piston packings, cylinder liner seals, valve stem seals, static valve stem seals, dynamic valve stem seals, automatic transmission front pump seals, rear axle pinion seals, universal joint gaskets, speedometer pinion seals, and foot brake pistons. Cups, O-rings and oil seals for torque transmission devices, seals and bearing seals for exhaust gas re-burning devices, hoses for re-burning devices, diaphragms for carburetor sensors, anti-vibration rubber (engine mounts, exhaust parts, muffler hangers, suspension bushings, center bearings, strut bumper rubber, etc.), anti-vibration rubber for suspension (strut mounts, bushings, etc.), anti-vibration rubber for drive systems (dampers, etc.), fuel hoses, EGR tubes and hoses, twin carburetor tubes, carburetor needle valve core valves, carburetor flange gaskets, oil hoses, oil cooler hoses, ATF hoses, cylinder head gaskets, water pump seals, gearbox seals, needle valve tips, motorcycle reed valve leads, automobile engine oil seals, gasoline hose gun seals, car air conditioner seals, rubber hoses for engine intercoolers, fuel supply line connector devices (fuel seals for automotive line connector systems, CAC valves, needle tips, engine wiring, filler hoses, car air conditioner O-rings, intake gaskets, fuel tank materials, distributor diaphragms, water hoses, clutch hoses, PS hoses, AT hoses, master back hoses, heater hoses, air conditioning hoses, ventilation hoses,Oil filler caps, PS rack seals, rack and pinion boots, CVJ boots, ball joint dust covers, strut dust covers, weather strips, glass runs, center unit gaskets, body site welts, bumper rubber, door latches, dash insulators, high tension cords, flat belts, poly V-belts, timing belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms and plungers for LPG vehicle regulators, diaphragms and valves for CNG vehicle regulators, DME compatible rubber parts, auto tensioner diaphragms and boots, idle speed control diaphragms and valves, auto speed control actuators, vacuum pump diaphragms, check valves and plungers, O.P.S. diaphragms and O-rings, gasoline pressure relief valves, engine cylinder sleeve O-rings and gaskets, wet cylinder sleeve O-rings and gaskets, differential gear seals and gaskets (gear oil seals and gaskets), power steering device seals and gaskets (PSF seals and gaskets), shock absorber seals and gaskets (SAF seals and gaskets), constant velocity joint seals and gaskets, wheel bearing seals and gaskets, metal gasket coating agents, caliper seals, boots, wheel bearing seals, and bladders used in tire vulcanization molding.

[0535] In the aircraft, space / rocket, and marine fields, the composition can be used particularly in fuel systems and lubricating oil systems. In the aircraft field, the composition can be used, for example, as various sealing parts for aircraft, various aircraft parts for aircraft engine oil applications, jet engine valve stem seals, gaskets, and O-rings, rotating shaft seals, gaskets for hydraulic equipment, firewall seals, fuel supply hoses, gaskets, and O-rings, aircraft cables, oil seals, and shaft seals.

[0536] In the space and rocket fields, the material can be used, for example, as lip seals, diaphragms, and O-rings for spacecraft, jet engines, missiles, etc., as O-rings for gas turbine engine oil, and as vibration isolation pads for missile ground control. In the marine field, the material can be used, for example, as screw propeller shaft stern seals, intake and exhaust valve stem seals for diesel engines, butterfly valve valve seals, butterfly valve valve seats and shaft seals, butterfly valve shaft seals, stern tube seals, fuel hoses, gaskets, engine O-rings, marine cables, marine oil seals, marine shaft seals, etc.

[0537] In the chemicals field such as the above-mentioned chemical plants and pharmaceuticals field, the material can be used in processes requiring high chemical resistance, for example, processes for producing chemicals such as pharmaceuticals, pesticides, paints, resins, etc. Specific uses in the above-mentioned chemicals and pharmaceuticals fields include seals used in chemical equipment, chemical pumps and flow meters, chemical piping, heat exchangers, pesticide sprayers, pesticide transfer pumps, gas piping, fuel cells, analytical equipment and physical and chemical equipment (e.g., column fittings for analytical equipment and instruments), shrinkage joints for flue gas desulfurization equipment, nitric acid plants, power plant turbines, etc., seals used in medical sterilization processes, plating solution seals, roller seals for papermaking belts, and wind tunnel joint seals; O-rings used in chemical equipment such as reactors and agitators, analytical equipment and instruments, chemical pumps, pump housings, valves, tachometers, etc., O-rings for mechanical seals, and O-rings for compressor sealing; packings used in high-temperature vacuum dryers, tube joints for gas chromatography and pH meters, etc., and glass cooling seals for sulfuric acid manufacturing equipment. Examples of suitable applications include: instrument packing; diaphragms used in diaphragm pumps, analytical equipment, and physical and chemical equipment; gaskets used in analytical equipment and meters; ferrules used in analytical equipment and meters; valve seats; U-cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., and corrosion-resistant linings for anodized aluminum tanks; coatings for plating masking jigs; valve parts for analytical equipment and physical and chemical equipment; expansion joints in flue gas desulfurization plants; acid-resistant hoses for concentrated sulfuric acid, etc., chlorine gas transfer hoses, oil-resistant hoses, and rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubing and medical tubing used in analytical equipment, physical and chemical equipment, etc.; trichlene-resistant rolls and dyeing rolls for textile dyeing; pharmaceutical stoppers; medical rubber stoppers; chemical solution bottles, chemical solution tanks, bags, chemical containers; and protective equipment such as strong acid-resistant and solvent-resistant gloves and boots.

[0538] In the photographic field such as the above-mentioned developing machines, the printing field such as printing machines, and the coating field such as coating equipment, the material can be used as rolls, belts, seals, valve parts, etc. in dry copiers. Specific uses in the above-mentioned photographic, printing, and coating fields include the surface layer of transfer rolls in copiers, cleaning blades in copiers, and belts in copiers; rolls (e.g., fixing rolls, pressure rolls, and pressure rolls) and belts for office automation equipment such as copiers, printers, and facsimiles; rolls, roll blades, and belts in PPC copiers; rolls in film developing machines and X-ray film developing machines; printing rolls, scrapers, tubes, valve parts, and belts for printing machines; ink tubes, rolls, and belts for printers; coating rolls, scrapers, tubes, and valve parts for coating and coating equipment; developing rolls, gravure rolls, guide rolls, guide rolls in magnetic tape production coating lines, and gravure rolls and coating rolls in magnetic tape production coating lines.

[0539] In the food equipment field, including the food plant equipment and household goods, the rubber can be used in food manufacturing processes, food transporters, and food storage devices. Specific uses in the food equipment field include seals for plate-type heat exchangers, solenoid valve seals for vending machines, packing for thermos pots, sanitary pipe packing, packing for pressure cookers, water heater seals, heat exchanger gaskets, diaphragms and packing for food processing equipment, and rubber materials for food processing machines (e.g., heat exchanger gaskets, various seals such as diaphragms and O-rings, piping, hoses, sanitary packing, valve packing, and filling packing used as a joint between the mouth of a bottle or the like and the filler during filling). Other examples include packing, gaskets, tubes, diaphragms, hoses, and joint sleeves used in products such as alcoholic beverages and soft drinks, filling equipment, food sterilization equipment, brewing equipment, water heaters, and various automatic food vending machines.

[0540] In the field of nuclear power plant equipment, the material can be used for check valves and pressure reducing valves around nuclear reactors, and seals for uranium hexafluoride enrichment equipment.

[0541] Specific uses in the above general industrial fields include sealing materials for hydraulic equipment such as machine tools, construction machinery, and hydraulic machinery; seals and bearing seals for hydraulic and lubricating machinery; sealing materials used for mandrels and the like; seals used for windows of dry cleaning equipment and the like; cyclotron seals and (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms for airborne sulfur dioxide and chlorine gas analyzers (pollution measuring instruments), snake pump linings, printing press rolls and belts, transport belts (conveyor belts), squeeze rolls for pickling iron plates and the like, robot cables, solvent squeeze rolls for aluminum rolling lines and the like, coupler O-rings, acid-resistant cushioning materials, dust seals and lip rubbers for sliding parts of cutting machinery, gaskets for food waste incineration machines, friction materials, metal or rubber surface modifiers, coating materials, and the like. It can also be used as gaskets and sealing materials for equipment used in papermaking processes, sealants for clean room filter units, construction sealants, protective coatings for concrete and cement, glass cloth impregnation materials, polyolefin processing aids, polyethylene moldability improving additives, fuel containers for small generators and lawn mowers, pre-coated metals obtained by applying a primer treatment to metal plates, etc. In addition, it can also be used as sheets and belts by impregnating woven fabric and baking it.

[0542] Specific examples of use in the steel industry include iron plate processing rolls in iron plate processing equipment.

[0543] Specific applications in the electrical field include insulating oil caps for bullet trains, venting seals for liquid-sealed transformers, transformer seals, oil well cable jackets, seals for ovens such as electric furnaces, window frame seals for microwave ovens, sealants used to bond the wedge and neck of a CRT, sealants for halogen lamps, fixing agents for electrical components, sealants for the terminal treatment of sheathed heaters, and sealants used for insulating and moisture-proofing the lead wire terminals of electrical equipment. The material can also be used as a coating material for oil-resistant and heat-resistant electric wires, highly heat-resistant electric wires, chemical-resistant electric wires, highly insulating electric wires, high-voltage power transmission lines, cables, electric wires used in geothermal power generation equipment, and electric wires used around automobile engines. It can also be used as an oil seal or shaft seal for vehicle cables. Furthermore, it can also be used as an electrical insulating material (e.g., insulating spacers for various electrical devices, insulating tapes for cable joints and ends, heat-shrinkable tubing, etc.), and as a material for electrical and electronic devices used in high-temperature atmospheres (e.g., motor lead wire materials, electric wire materials for high-temperature furnaces), as well as a sealing layer or protective film (back sheet) for solar cells.

[0544] In the field of fuel cells, the material can be used as a sealing material between electrodes and between electrodes and separators in polymer electrolyte fuel cells, phosphate fuel cells, etc., as well as seals, packings, and separators for piping for hydrogen, oxygen, generated water, etc.

[0545] In the field of electronic components, it can be used as a heat dissipation material raw material, an electromagnetic wave shielding material raw material, a gasket for computer hard disk drives (magnetic recording devices), etc. It can also be used as a rubber cushion (crash stopper) for hard disk drives, a binder for electrode active materials in nickel-metal hydride secondary batteries, a binder for active materials in lithium-ion batteries, a polymer electrolyte for lithium secondary batteries, a binder for the positive electrodes of alkaline storage batteries, a binder for EL elements (electroluminescence elements), a binder for electrode active materials in capacitors, a sealant, a sealing agent, a quartz coating material for optical fiber, a film or sheet such as an optical fiber coating material, potting, coating, or adhesive seal for electronic components and circuit boards, a fixing agent for electronic components, a modifying agent for sealants such as epoxy, a coating agent for printed circuit boards, a modifying agent for printed wiring board prepreg resins such as epoxy, a shatterproof material for light bulbs, a computer gasket, a large computer cooling hose, a packing such as a gasket or O-ring for secondary batteries, particularly lithium secondary batteries, a sealing layer covering one or both outer surfaces of an organic EL structure, a connector, a damper, etc.

[0546] In the field of chemical transport equipment, it can be used as a safety valve or shipping valve for trucks, trailers, tank trucks, ships, etc.

[0547] In the field of mining equipment parts for exploration for energy resources such as oil and gas, they are used as various sealing materials used in mining oil, natural gas, etc., boots for electrical connectors used in oil wells, etc. Specific uses in the field of mining equipment parts for exploration for energy resources include drill bit seals, pressure adjustment diaphragms, seals for horizontal drilling motors (stators), stator bearing (shaft) seals, sealing materials used in blowout preventers (BOPs), sealing materials used in rotary blowout preventers (pipe wipers), sealing materials and gas-liquid connectors used in MWDs (real-time drilling information detection systems), logging tool seals (e.g., O-rings, seals, packings, gas-liquid connectors, boots, etc.) used in logging equipment, expansion packers and completion packers and packer seals used therein, seals, packings, and perforators used in cementing equipment. Examples of seals include seals used in drilling equipment, seals, packings and motor linings used in mud pumps, underground audiometer covers, U-cups, composition seating cups, rotary seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valve seals, seals for hydraulic fracturing equipment, seals and packings for linear packers and linear hangers, wellhead seals and packings, seals and packings for chokes and valves, sealing materials for LWD (logging while drilling), diaphragms used in oil exploration and oil drilling applications (for example, diaphragms for supplying lubricating oil to oil drilling pits, etc.), gate valves, electronic boots, and sealing elements for drilling guns.

[0548] Other applications include joint seals for kitchens, bathrooms, washrooms, etc.; cover cloths for outdoor tents; seals for printing materials; rubber hoses for gas heat pumps, fluorocarbon-resistant rubber hoses; agricultural films, linings, and weather-resistant covers; and tanks made of laminated steel sheets used in the construction and home appliance fields.

[0549] Furthermore, it can be used as an article bonded to a metal such as aluminum. Examples of such uses include door seals, gate valves, pendulum valves, solenoid tips, as well as metal-rubber parts bonded to metals such as piston seals, diaphragms, and metal gaskets. It can also be used in rubber parts, brake shoes, brake pads, etc. for bicycles.

[0550] Furthermore, one form of the crosslinked article of the present disclosure is a belt. Examples of such belts include the following: power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.); conveyor belts (conveyor belts) used in various high-temperature locations, such as around the engines of agricultural machinery, machine tools, industrial machinery, etc.; conveyor belts for transporting loose or granular materials, such as coal, crushed stone, soil and sand, ore, and wood chips, in high-temperature environments; conveyor belts used in steelworks such as blast furnaces; conveyor belts for applications exposed to high-temperature environments, such as precision equipment assembly factories and food factories; V-belts and V-ribbed belts for agricultural machinery, general equipment (e.g., office automation equipment, printing machines, commercial dryers, etc.), automobiles, etc.; transmission belts for transport robots; toothed belts such as transmission belts for food machinery and machine tools; toothed belts used in automobiles, office automation equipment, medical applications, printing machines, etc. In particular, timing belts are representative of toothed belts for automobiles.

[0551] The belt may have a single layer structure or a multilayer structure. In the case of a multilayer structure, the belt may be composed of a layer obtained by crosslinking the crosslinkable composition of the present disclosure and a layer made of another material. In a multilayer belt, the layer made of another material may include a layer made of another rubber, a layer made of a thermoplastic resin, various fiber reinforcement layers, canvas, a metal foil layer, etc.

[0552] The crosslinked product of the present disclosure can also be used for industrial vibration-damping pads, vibration-damping mats, railway slab mats, pads, automotive vibration-damping rubber, etc. Automotive vibration-damping rubber includes vibration-damping rubber for engine mounts, motor mounts, member mounts, strut mounts, bushings, dampers, muffler hangers, center bearings, etc.

[0553] Other uses include joint members such as flexible joints and expansion joints, boots, grommets, etc. In the marine field, examples include marine pumps, etc. Joint members are connectors used in piping and piping equipment, and are used for preventing vibration and noise generated from piping systems, absorbing expansion and contraction and displacement due to temperature and pressure changes, absorbing dimensional fluctuations, and mitigating or preventing the effects of earthquakes and ground subsidence. Flexible joints and expansion joints can be preferably used as complex-shaped molded articles for, for example, shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering and water supply piping, and automobiles. The boots can be preferably used as complex shaped molded articles such as automobile boots such as constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, and piston boots, as well as various industrial boots such as boots for agricultural machinery, boots for industrial vehicles, boots for construction machinery, boots for hydraulic machinery, boots for pneumatic machinery, boots for centralized lubricators, boots for transferring liquids, boots for firefighting, and boots for transferring various liquefied gases.

[0554] The crosslinked product of the present disclosure can also be used as a diaphragm for a filter press, a diaphragm for a blower, a diaphragm for a water supply, a diaphragm for a liquid storage tank, a diaphragm for a pressure switch, a diaphragm for an accumulator, or a diaphragm for an air spring in a suspension or the like.

[0555] By adding the crosslinked product of the present disclosure to rubber or resin, an anti-slip agent can be obtained that provides molded articles or coating films that are non-slip in wet environments such as rain, snow, ice, and sweat.

[0556] Furthermore, the crosslinked product of the present disclosure 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, and the like, using, for example, melamine resin, phenolic resin, epoxy resin, or the like.

[0557] The crosslinked materials of the present disclosure can also contribute to impermeability of various substrates, such as weapon-related sealing gaskets and protective clothing against contact with aggressive chemical agents.

[0558] The compound can also be used in various sealing materials, such as O-rings, V-rings, X-rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals, and other sealing materials used to seal lubricating oils (engine oils, transmission oils, gear oils, etc.) containing amine additives (particularly amine additives used as antioxidants and detergents / dispersants) used in transportation such as automobiles and ships, as well as tubes, hoses, various rubber rolls, coatings, belts, valve bodies, etc. The compound can also be used as a laminating material and a lining material.

[0559] The coating material can be used as a heat-resistant and oil-resistant wire coating material for lead wires of sensors that come into contact with transmission oil and / or engine oil in internal combustion engines of automobiles, etc. to detect the oil temperature and / or oil pressure, and can also be used in high-temperature oil atmospheres such as the oil pans of automatic transmissions and engines.

[0560] In addition, the crosslinked product of the present disclosure may be used by forming a vulcanized coating. Specific examples of uses include non-adhesive, oil-resistant rolls for copiers, weather-resistant anti-icing weather strips, rubber stoppers for infusions, rubber vial stoppers, mold release agents, non-adhesive light-duty conveying belts, anti-adhesive coatings for car engine mount gaskets, coatings for synthetic fibers, and bolt members or joints with a thin packing coating layer.

[0561] The use of the crosslinked product of the present disclosure for automobile-related parts also includes use for parts of motorcycles having a similar structure. Examples of fuels used in the automobile-related fields include diesel oil, gasoline, and diesel engine fuels (including biodiesel fuels).

[0562] In addition to being used as a crosslinked product after crosslinking, the crosslinkable composition of the present disclosure can also be used as various parts in various industrial fields. Therefore, next, applications of the crosslinkable composition of the present disclosure will be described. The crosslinkable composition of the present disclosure can be used for surface modifiers for metals, rubber, plastics, glass, etc.; sealing materials and coating materials that require heat resistance, chemical resistance, oil resistance, and non-stickiness, such as metal gaskets and oil seals; non-stick coating materials or bleed barriers for office equipment rolls and office equipment belts; and coatings by impregnation or baking onto woven fabric sheets and belts. The crosslinkable composition of the present disclosure can be used as a sealing material, lining, or sealant with complex shapes by conventional methods by increasing its viscosity and concentration; can be used to form thin films of several microns by decreasing its viscosity; and can be used to coat pre-coated metals, O-rings, diaphragms, and reed valves by increasing its viscosity. It can also be used to coat woven fabric or paper transport rolls or belts, printing belts, chemical-resistant tubes, chemical stoppers, fuel hoses, and the like.

[0563] Examples of substrates that can be coated with the crosslinkable composition of the present disclosure include metals such as iron, stainless steel, copper, aluminum, and brass; glass products such as glass plates and woven and nonwoven glass fiber fabrics; molded articles and coated products made of general-purpose and heat-resistant resins such as polypropylene, polyoxymethylene, polyimide, polyamideimide, polysulfone, polyethersulfone, and polyetheretherketone; molded articles and coated products made of general-purpose rubbers such as SBR, butyl rubber, NBR, and EPDM, and heat-resistant rubbers such as silicone rubber and fluororubber; woven and nonwoven fabrics made of natural and synthetic fibers; etc. Coatings formed from the crosslinkable composition of the present disclosure can be used in fields requiring heat resistance, solvent resistance, lubricity, and non-stick properties, and specific applications include rolls (e.g., fuser rolls and pressure rolls) and conveyor belts for office automation equipment such as copiers, printers, and facsimiles; sheets and belts; O-rings, diaphragms, chemical-resistant tubes, fuel hoses, valve seals, gaskets for chemical plants, and engine gaskets.

[0564] The crosslinkable composition of the present disclosure can also be dissolved in a solvent and used as a paint or adhesive. It can also be used as a paint in the form of an emulsified dispersion (latex). The composition is used as a sealant or lining for various devices and pipes, or as a surface treatment agent for structures made of inorganic and organic substrates such as metal, ceramics, glass, stone, concrete, plastic, rubber, wood, paper, and fiber. The composition can be applied to substrates by dispenser coating or screen printing.

[0565] The crosslinkable compositions of the present disclosure may be used as coating compositions for casting films or for dipping substrates such as fabrics, plastics, metals, or elastomers. In particular, the crosslinkable compositions of the present disclosure may be used in the form of latexes to produce coated fabrics, protective gloves, impregnated textiles, O-ring coatings, fuel system quick connect O-ring coatings, fuel system seal coatings, fuel tank rollover valve diaphragm coatings, fuel tank pressure sensor diaphragm coatings, oil filter and fuel filter seal coatings, fuel tank sender seal and sender head fitting seal coatings, copier fuser roll coatings, and polymer coating compositions. They are useful for coating silicone rubber, nitrile rubber, and other elastomers. They are also useful for coating parts made from such elastomers to enhance both the permeation resistance and chemical resistance of the substrate elastomer as well as its thermal stability. Other applications include coatings for heat exchangers, expansion joints, vats, tanks, fans, flue ducts and other ductwork, and containment structures, such as concrete containment structures. The compositions may be applied to exposed cross sections of multilayer component structures, for example, in the manufacturing processes of hose construction and diaphragms. Sealing members in connections and joints are often composed of hard materials, and the crosslinkable compositions of the present disclosure provide improved frictional interfaces, enhanced dimensional interference fits with reduced leakage along the sealing surfaces. The latexes enhance seal durability in various automotive system applications. They can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any joint where hoses and tubing are connected to another component. An additional utility of the compositions is in repairing manufacturing defects (and damage caused by use) in multilayer rubber structures, such as three-layer fuel hoses. The compositions are also useful for coating thin steel sheets, which may be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel can be assembled to create a gasket between two rigid metal components.The sealing effect is achieved by applying the crosslinkable composition of the present disclosure between the layers. This process can be used to manufacture engine head gaskets and exhaust manifold gaskets for the purpose of reducing bolt forces and strain on assembled parts while providing good fuel economy and low emissions due to low cracks, deflections, and hole distortions.

[0566] The crosslinkable composition of the present disclosure can also be used as a coating agent; a substrate-integrated gasket or packing formed by dispenser molding on a substrate containing an inorganic material such as a metal or ceramic; or a multi-layer product formed by coating a substrate containing an inorganic material such as a metal or ceramic.

[0567] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0568] <1> According to a first aspect of the present disclosure, there is provided a composition comprising a polymer (I) containing polymerized units (I) based on a monomer (I) represented by general formula (I) and a fluororubber, wherein the content of the polymer (I) is 0.0001 to 1.0 mass% relative to the fluororubber. １ X ３ =CX ２ R (-CZ １ Z ２ -A ０ ) ｍ (I) (wherein, X １ and X ３ are each independently F, Cl, H or CF ３ and X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is an anionic group; R is a linking group; Z １ and Z ２are each independently H, F, an alkyl group, or a fluorine-containing alkyl group; and m is an integer of 1 or more.) <2> According to a second aspect of the present disclosure, there is provided a composition according to the first aspect, in which the polymer (I) is a polymer (2) containing polymerized units (2) based on a monomer (2) represented by general formula (2). CX ２ =CY(-O-Rf-A) (2) (wherein X may be the same or different and is -H or F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond or a keto group; A is -COOM, -SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium, or optionally substituted phosphonium, and R ７is H or an organic group.) <3> According to a third aspect of the present disclosure, there is provided a composition according to the first or second aspect, in which the fluororubber is a perfluoroelastomer. <4> According to a fourth aspect of the present disclosure, there is provided a composition according to any of the first to third aspects, which is substantially free of a fluorinated surfactant. <5> According to a fifth aspect of the present disclosure, there is provided a composition according to any of the first to fourth aspects, which is obtained by preparing a polymerization dispersion containing polymer (I), the fluororubber, and an aqueous medium, and contacting the fluororubber in the polymerization dispersion with an alcohol having 3 to 6 carbon atoms per OH group to coagulate the fluororubber. <6> According to a sixth aspect of the present disclosure, there is provided a composition according to the fifth aspect, in which the alcohol has 3 to 5 carbon atoms per OH group. <7> According to a seventh aspect of the present disclosure, there is provided a composition according to the fifth or sixth aspect, in which the alcohol has a MolLogP value within the range of 0.3 to 1.6. <8> According to an eighth aspect of the present disclosure, there is provided a composition according to any of the first to fourth aspects, obtained by preparing a polymerization dispersion containing polymer (I), the fluororubber, and an aqueous medium, and freezing the polymerization dispersion to coagulate the fluororubber. <9> According to a ninth aspect of the present disclosure, there is provided a composition according to any of the first to fourth aspects, obtained by preparing a polymerization dispersion containing polymer (I), the fluororubber, and an aqueous medium, and contacting the fluororubber in the polymerization dispersion with at least one organic solvent selected from the group consisting of the following compounds to coagulate the fluororubber: C2 to C5 carboxylic acid, methyl ethyl ketone, methyl acetate, dimethyl carbonate, acetone, 3-methyl-2-cyclopentenone, methyl propionate, ethyl acetate, tetrahydrofuran, 1,2-dimethoxyethane. <10> According to a tenth aspect of the present disclosure, there is provided a crosslinkable composition containing the composition according to any of the first to ninth aspects and at least one selected from the group consisting of an inorganic nitride, an organotin compound, an ammonia-generating compound, and a crosslinking agent.<11> According to an eleventh aspect of the present disclosure, there is provided a crosslinkable composition according to the tenth aspect, which contains a perfluoroelastomer having an iodine atom or a bromine atom as the fluororubber. <12> According to a twelfth aspect of the present disclosure, there is provided a crosslinkable composition according to the eleventh aspect, which contains an organic peroxide as the crosslinking agent and further contains a crosslinking coagent. <13> According to a thirteenth aspect of the present disclosure, there is provided a crosslinkable composition according to the eleventh or twelfth aspect, wherein the perfluoroelastomer is at least one selected from the group consisting of tetrafluoroethylene / perfluorovinyl ether copolymer represented by general formula (140), tetrafluoroethylene / fluoromonomer copolymer represented by general formula (140) / monomer copolymer having an iodine atom or a bromine atom, tetrafluoroethylene / fluoromonomer copolymer represented by general formula (160), and tetrafluoroethylene / fluoromonomer copolymer represented by general formula (160) / monomer copolymer having an iodine atom or a bromine atom. General formula (140): CF. ２ = CFO (CF ２ CF (Y １４１ ) O) ｍ (CF ２ ) ｎ F (wherein, Y １４１ represents a fluorine atom or a trifluoromethyl group. m is an integer of 1 to 4. n is an integer of 1 to 4.) General formula (160): CF ２ =CF-ORf １６１ (wherein, Rf １６１ represents a perfluoroalkyl group having 1 to 10 carbon atoms.) <14> According to a fourteenth aspect of the present disclosure, there is provided a crosslinkable composition according to the tenth aspect, containing a perfluoroelastomer having a cyano group as the fluororubber. <15> According to a fifteenth aspect of the present disclosure, there is provided a crosslinkable composition comprising an inorganic nitride, an organotin compound, a compound capable of generating ammonia, a compound having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, and a compound represented by the general formula (47): (In the formula, R ４１ , R ４２ and R ４３A crosslinkable composition according to a fourteenth aspect is provided, which contains at least one compound selected from the group consisting of compounds represented by the general formula (140): CF ２ = CFO (CF ２ CF (Y １４１ ) O) ｍ (CF ２ ) ｎ F (wherein, Y １４１ represents a fluorine atom or a trifluoromethyl group. m is an integer of 1 to 4. n is an integer of 1 to 4.) General formula (160): CF ２ =CF-ORf １６１ (wherein, Rf １６１ represents a perfluoroalkyl group having 1 to 10 carbon atoms.) <17> According to a seventeenth aspect of the present disclosure, there is provided a crosslinked product obtained by crosslinking the crosslinkable composition according to any one of the tenth to sixteenth aspects.

[0569] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0570] The values ​​in the examples were measured by the following methods.

[0571] (Content of Polymer (I) in Dry Fluororubber) A predetermined amount of Polymer (I) was added to fluororubber not containing Polymer (I) and dispersed well. The obtained fluororubber was molded into a film and measured with a Fourier transform infrared spectrometer (manufactured by PerkinElmer). Absorption wavelength - CF (2213 to 2685 cm －１ ) and -COO (1600-1827 cm －１The ratio of the absorbance area of ​​each of the polymers (I) was measured, and a calibration curve was created from the amount of polymer (I) added. The fluororubbers obtained in the examples and comparative examples were similarly measured, and the content of polymer (I) was calculated from the calibration curve.

[0572] (Polymer composition ratio) １９ Measurements were made by F-NMR (solid-state NMR) and Fourier transform infrared spectrophotometer (FT-IR).

[0573] (Iodine Atom Content) It was measured by elemental analysis.

[0574] (Mooney Viscosity) Measurement was carried out using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES at 170°C or 100°C in accordance with JIS K6300.

[0575] (Glass Transition Temperature) A differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo) was used to obtain a DSC curve by heating 10 mg of a sample at a rate of 10°C / min, and the peak top temperature of the differential curve specified in JIS K6240 was taken as the glass transition temperature.

[0576] Examples 1 to 7 and 10 to 11 These examples show examples in which fluororubber is coagulated by coagulation method (1) or coagulation method (3).

[0577] 0.062 g of polymer (A) (formula: CF ２ = CFOCF ２ CF ２ 18 g of a polymer dispersion (1.8 g of TFE / PMVE copolymer content) containing a TFE / PMVE copolymer (polymer composition ratio TFE / PMVE=60 / 40 mol%) containing a homopolymer of monomer A represented by COOH neutralized with aqueous ammonia was added dropwise to 10 g of an alcohol or organic solvent having 3 to 6 carbon atoms per OH group to coagulate a fluororubber. After washing with water, the mixture was dried at 75°C for 20 hours. The dried fluororubber obtained was molded into a film, and the content of polymer (A) was measured using a Fourier transform infrared spectrometer.

[0578] Examples 8-9 These examples show examples of coagulating fluororubber by the coagulation method (2).

[0579] To 20 g of the same polymer dispersion as in Examples 1 to 7 and 10 to 11 (TFE / PMVE copolymer content: 2.0 g), 0.9 g of the alcohol or organic solvent indicated in coagulation method (1) or (3) was added, and the mixture was frozen in a freezer (-25°C) for 16 hours, and then thawed by contact with water at 40°C to obtain a coagulated rubber. After washing with water, the mixture was dried at 75°C for 20 hours. The obtained dried fluororubber was molded into a film, and the content of polymer (I) was measured using a Fourier transform infrared spectrometer.

[0580] Example 12 In this example, an example of coagulating fluororubber by the coagulation method (1) is shown.

[0581] 0.048 g of polymer (B) (formula: CF ２ = CFOCF ２ CF ２ SO ３ NH ４ 18 g of a polymer dispersion (TFE / PMVE copolymer content: 1.8 g) containing a TFE / PMVE copolymer (polymer composition ratio TFE / PMVE=61 / 39 mol%) containing a homopolymer of monomer B represented by the formula (B) was added dropwise to 10 g of 2-butanol to coagulate a fluororubber. After washing with water, the mixture was dried at 140°C for 12 hours. The content of polymer (B) in the resulting dried fluororubber was measured by NMR.

[0582] Comparative Example 1 23 g of the same polymer dispersion as in Examples 1 to 7 and 10 to 11 (TFE / PMVE copolymer content: 2.3 g) was added dropwise to 30 g of 20% nitric acid to coagulate a fluororubber. After washing with water, it was dried at 75°C for 20 hours. The obtained dried fluororubber was molded into a film, and the content of polymer (A) was measured using a Fourier transform infrared spectrometer.

[0583] The results are shown in Table 1.

[0584] Preparation Example 1 The amount of deionized water initially charged as described in WO 2022-107890 was 1561.5 g, and the polymer B aqueous solution B-2 was changed to 992.5 g of polymer F aqueous solution F-2 (solid content concentration: 2.65 mass%). Except for this, polymerization was carried out in the same manner as in Example 11 described in WO 2022-107890, and 4027 g of an aqueous dispersion having a solid content concentration of 31.5 mass% was obtained. The polymerization time was 69.4 hours.

[0585] The resulting dispersion was post-treated by the method of Comparative Example 2 of the present application to obtain 170 g of perfluoroelastomer. Analysis of the resulting perfluoroelastomer gave the following results: Perfluoroelastomer composition: TFE / PMVE = 66.3 / 33.7 mol % Iodine content: 0.44 mass % Mooney viscosity: ML1+10(100°C) = 63.8 Glass transition temperature: -1.3°C

[0586] Example 13 The same procedure as in Example 11 described in WO 2022-107890 was carried out, and 850 g of the resulting emulsion dispersion was adjusted with water to the solids concentration shown in Table 2 to prepare a dispersion. This dispersion was added dropwise to 359 g of 2-BuOH adjusted to 71% with water to cause coagulation. The fluororubber was separated by filtration and washed with water as shown in Table 2. That is, the fluororubber was washed four times using 1,360 g of water. The separated fluororubber was then vacuum dried at 140°C for 12 hours.

[0587] Example 14 Coagulation and drying were carried out in the same manner as in Example 13, except that the emulsified dispersion obtained in Preparation Example 1 was used.

[0588] Example 15 The same procedure as in Example 4 described in WO 2022-107890 was carried out to prepare 1700 g of an emulsion dispersion whose solids concentration was adjusted with water to the concentration shown in Table 3. This dispersion was added dropwise to 718 g of 2-BuOH adjusted to 71% with water to cause coagulation. The fluororubber was filtered off and washed with water as shown in Table 3. The filtered fluororubber was then vacuum dried at 70°C for 24 hours.

[0589] Example 16 The same procedure as in Example 15 was carried out, except that the dispersion obtained in Example 13 described in WO 2022-107890 was used.

[0590] Comparative Example 2 566 g of an emulsified dispersion obtained by the same procedure as in Example 11 described in WO 2022-107890 was adjusted with water to the solids concentration shown in Table 2, and this dispersion was added dropwise to 4,000 g of a 10% aqueous hydrochloric acid solution while stirring. The precipitated fluororubber was filtered off and washed with water as shown in Table 2. The filtered fluororubber was then vacuum dried at 140°C for 12 hours.

[0591] Comparative Example 3 The same procedure as in Comparative Example 2 was carried out, except that the dispersion obtained in Preparation Example 1 was used.

[0592] Comparative Example 4 850 g of an emulsified dispersion obtained by the same procedure as in Example 4 described in WO 2022-107890 was adjusted with water to the solids concentration shown in Table 3, and this dispersion was added dropwise to 4,000 g of a 10% aqueous hydrochloric acid solution while stirring. The precipitated fluororubber was filtered off and washed with water as shown in Table 3. The filtered fluororubber was then vacuum dried at 70°C for 24 hours.

[0593] Comparative Example 5 The same operation as in Comparative Example 4 was carried out, except that the emulsified dispersion obtained by carrying out the same operation as in Example 13 described in WO 2022-107890 was used.

[0594] A crosslinkable fluororubber composition was prepared by compounding 100 parts by mass of the fluororubbers obtained in Examples 13 and 14 and Comparative Examples 2 and 3 with 2 parts by mass of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Chemical Co., Ltd.) as a crosslinking agent, 1 part by mass of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (Perhexa 25B, manufactured by NOF Corporation), and 15 parts by mass of carbon black (Thermax N-990, manufactured by Cancarb Co., Ltd.) as a filler, and kneading the mixture with an open roll.

[0595] The obtained fluororubber composition was pressed at 160°C for 30 minutes to crosslink, and then further subjected to oven crosslinking at 180°C for 4 hours to produce a crosslinked product and an O-ring (P-24) with a thickness of 2 mm. Various physical properties of the fluororubber composition and the crosslinked product were measured by the following methods. The results are shown in Table 2.

[0596]

[0597] <Crosslinkability> For the fluororubber composition, a crosslinking curve was obtained at the same temperature as press crosslinking using an RPA2000 manufactured by ALPHA TECHNOLOGIES, and the optimum crosslinking time (T90) was determined. <Normal Physical Properties> Using a 2 mm thick crosslinked product, M100 (100% modulus, MPa), TB (tensile strength at break, MPa), and tensile elongation at break (EB, %) were measured in accordance with JIS-K6251. <Hardness> Using a 2 mm thick crosslinked product, hardness (Shore A) was measured (peak value) in accordance with JIS-K6253. <Compression Set> Compression set was measured using an O-ring under the conditions shown in Tables 2 and 3 in accordance with the method described in ASTM D395 or JIS K6262.

[0598] A crosslinkable fluororubber composition was prepared by blending 100 parts by mass of the fluororubbers obtained in Examples 15 and 16 and Comparative Examples 4 and 5 with 2 parts by mass of 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane (AFTA-PH) as a crosslinking agent and 5 parts by mass of calcium oxide (CML#35, manufactured by Omi Chemical Industry Co., Ltd.), and kneading the mixture with an open roll.

[0599] The obtained fluororubber composition was pressed at 180°C for 40 minutes to crosslink, and then further subjected to oven crosslinking at 290°C for 18 hours to produce a crosslinked product having a thickness of 2 mm and an O-ring (P-24). The results of various physical properties of the fluororubber composition and the crosslinked product are shown in Table 3.

[0600]

Claims

1. A composition comprising a polymer (I) containing polymerization units (I) based on a monomer (I) represented by general formula (I) and a fluororubber, wherein the content of the polymer (I) is 0.0001 to 1.0 mass % relative to the fluororubber. CX １ X ３ =CX ２ R(-CZ １ Z ２ -A ０ ) ｍ (I) (In the formula, X １ and X ３ are each independently F, Cl, H or CF ３ and X ２ is H, F, an alkyl group or a fluorine-containing alkyl group; A ０ is an anionic group; R is a linking group; Z １ and Z ２ are each independently H, F, an alkyl group or a fluorine-containing alkyl group; and m is an integer of 1 or more.

2. 2. The composition according to claim 1, wherein the polymer (I) is a polymer (2) containing polymerization units (2) based on a monomer (2) represented by general formula (2). CX ２ =CY(-O-Rf-A) (2) (In the formula, X may be the same or different and is -H or F; Y is -H, -F, an alkyl group or a fluorine-containing alkyl group; Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond or a keto group having 2 to 100 carbon atoms; A is -COOM, -SO ３ M, -OSO ３ M or -C(CF ３ ) ２ OM (M is H, metal atom, NR ７ ４ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium; R ７ is H or an organic group.

3. 3. The composition according to claim 1, wherein the fluororubber is a perfluoroelastomer.

4. The composition according to claim 1 or 2, which is substantially free of a fluorine-containing surfactant.

5. A polymerization dispersion containing the polymer (I), the fluororubber, and an aqueous medium is prepared, The composition according to claim 1 or 2, which is obtained by contacting the fluororubber in the polymerization dispersion with an alcohol having 3 to 6 carbon atoms per OH group to coagulate the fluororubber.

6. The composition according to claim 5, wherein the alcohol has 3 to 5 carbon atoms per OH group.

7. 6. The composition of claim 5, wherein the alcohol has a MolLogP in the range of 0.3 to 1.

6.

8. A polymerization dispersion containing the polymer (I), the fluororubber, and an aqueous medium is prepared, The composition according to claim 1 or 2, which is obtained by freezing the polymer dispersion to coagulate the fluororubber.

9. A polymerization dispersion containing the polymer (I), the fluororubber, and an aqueous medium is prepared, The composition according to claim 1 or 2, obtained by contacting the fluororubber in the polymerization dispersion with at least one organic solvent selected from the group consisting of the following compounds, to coagulate the fluororubber: Carboxylic acids with 2 to 5 carbon atoms Methyl Ethyl Ketone Methyl acetate Dimethyl carbonate acetone 3-Methyl-2-cyclopentenone Methyl propionate Ethyl acetate Tetrahydrofuran 1,2-Dimethoxyethane

10. A crosslinkable composition comprising the composition according to claim 1 or 2 and at least one member selected from the group consisting of inorganic nitrides, organotin compounds, compounds that generate ammonia, and crosslinking agents.

11. The crosslinkable composition according to claim 10, comprising a perfluoroelastomer having an iodine atom or a bromine atom as the fluororubber.

12. The crosslinkable composition according to claim 11, which contains an organic peroxide as a crosslinking agent and further contains a crosslinking assistant.

13. The perfluoroelastomer is at least one selected from the group consisting of tetrafluoroethylene / perfluorovinyl ether copolymer represented by the general formula (140), tetrafluoroethylene / fluoromonomer / monomer copolymer having an iodine atom or a bromine atom represented by the general formula (140), tetrafluoroethylene / fluoromonomer copolymer represented by the general formula (160), and tetrafluoroethylene / fluoromonomer / monomer copolymer having an iodine atom or a bromine atom represented by the general formula (160). The crosslinkable composition according to claim 11. General formula (140): CF ２ = CFO(CF ２ CF(Y １４１ ))O ｍ (CF ２ ) ｎ F (In the formula, Y １４１ represents a fluorine atom or a trifluoromethyl group; m is an integer from 1 to 4; and n is an integer from 1 to 4. General formula (160): CF ２ = CF-ORf １６１ (wherein, Rf １６１ represents a perfluoroalkyl group having 1 to 10 carbon atoms.

14. Contains perfluoroelastomer having cyano group as fluororubber The crosslinkable composition according to claim 10.

15. Inorganic nitrides, organotin compounds, compounds capable of generating ammonia, compounds having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, and compounds represented by the general formula (47): 【Chemical 39】 (In the formula, R 41 represents -SO 2 -, -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms or a single bond, or 【Chemistry 40】 The crosslinkable composition according to claim 14, which contains at least one compound selected from the group consisting of compounds represented by the following formula:

16. The crosslinkable composition according to claim 14, wherein the perfluoroelastomer is at least one selected from the group consisting of tetrafluoroethylene / fluoromonomer represented by general formula (140) / monomer copolymer having a cyano group, and tetrafluoroethylene / fluoromonomer represented by general formula (160) / monomer copolymer having a cyano group. General formula (140): CF ２ = CFO(CF ２ CF(Y １４１ )O) ｍ (CF ２ ) ｎ F (In the formula, Y １４１ represents a fluorine atom or a trifluoromethyl group; m is an integer from 1 to 4; and n is an integer from 1 to 4. General formula (160): CF ２ = CF-ORf １６１ (wherein, Rf １６１ represents a perfluoroalkyl group having 1 to 10 carbon atoms.

17. A crosslinked product obtained by crosslinking the crosslinkable composition according to claim 10.

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